JP2022103983A - Rubber composition, tire, and rubber additive - Google Patents

Abstract

To provide a rubber composition that has sufficient low heat generation and excellent processability.SOLUTION: Provided is a rubber composition that contains the following components (a), (b) and (c). Component (a): a rubber component; Component (b): a compound represented by the following formula (1); Component (c): a compound represented by the following formula (2). (1) X-CO-NH-A (2) Z-CO-NH-A [In the formula, A indicates the group represented by the formula (i) -NR1R2 or the formula (ii) -N=R3R4, in formula (i) or (ii), R1 to R4 are hydrogen or an alkyl of 1 to 18 carbon atoms, X is a nitrogen-containing heterocyclic group, an alkyl of 1 to 5 carbon atoms, an aryl or a group -Y-CO-NHA, or may form a ring. Y is a divalent nitrogen-containing heterocyclic group, an alkylene of 1 to 18 carbon atoms, or an arylene, and Z is an alkyl of 6 to 40 carbon atoms.].SELECTED DRAWING: None

Description

The present invention relates to rubber compositions, tires, and rubber additives.

In recent years, from the viewpoints of resource saving, energy saving, and environmental protection, regulations on carbon dioxide and other exhaust gases have become stricter, and there is an increasing demand for fuel efficiency of automobiles. While the drive system and transmission system of the engine etc. contribute greatly to the fuel efficiency of automobiles, the rolling resistance of the tire is also greatly involved, so not only the drive system and transmission system but also the rolling resistance of the tire is improved. Is also needed.

As a method for improving the rolling resistance of a tire, a method of blending a hydrazide compound or a hydrazone compound in a rubber composition is known (Patent Document 1).

However, when a hydrazide compound or a hydrazone compound is blended in a rubber composition, the low heat generation property is improved, while the viscosity (Moony viscosity) of the rubber composition tends to increase, resulting in deterioration of workability. There is.

Japanese Unexamined Patent Publication No. 8-27315

In view of the above circumstances, an object of the present invention is to provide a rubber composition having sufficiently low heat generation properties and excellent processability.

As a result of diligent research to solve the above problems, the present inventor maintains the low heat build-up effect originally possessed by the compound represented by the formula (1) by adding a predetermined compound to the rubber component. At the same time, it has been found that an increase in Mooney viscosity can be suppressed and a rubber composition having excellent processability can be obtained. The present inventor has further studied based on such findings and has completed the present invention.

〔式中、Ａは下記式（i）又は（ii）で示される基を示す。
式（i）又は（ii）において、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、各々水素原子又は炭素数１～１８のアルキル基を示す。
Ｘは、窒素含有複素環基、炭素数１～５のアルキル基、アリール基、又は基－Ｙ－ＣＯ－ＮＨＡを示す。或いは、Ｘは、基－ＣＨＲ^６－ＣＲ^５＝Ｎ－を介してＡと結合することにより環を形成してもよい。これら各基及び環は、さらに置換基を有していてもよい。
Ｙは、２価の窒素含有複素環基、炭素数１～１８のアルキレン基、又はアリーレン基を示す。
Ｒ^５は、水素原子、炭素数１～１８のアルキル基、又はアリール基を、
Ｒ^６は、水素原子、ハロゲン原子、アルキル基、アルケニル基、ヒドラジド基、アミノ基、チオカルボキシル基、又はチオール基を示し、これら各基は更に置換基を有していてもよい。
Ｚは、炭素数６～４０のアルキル基を示し、該アルキル基はさらに置換基を有していてもよい。〕

項２．
前記式（１）で表される化合物は、下記式（1ａ）、（１ｂ）、及び（１ｃ）で表される化合物からなる群より選択される少なくとも一種である、請求項１に記載のゴム組成物。

〔式中、Ｘ´は窒素含有複素環基、炭素数１～５のアルキル基、又はアリール基を示す。
Ｙ´は２価の窒素含有複素環基、炭素数１～１８のアルキレン基、又はアリーレン基を示す。
Ｘ´及びＹ´で示される各基は、さらに置換基を有していてもよい。
Ａ、Ｒ^５、及びＲ^６は前記に同じである。〕
項３．
前記式（１）においてＸで示される窒素含有複素環基及び式（１ａ）においてＸ´で示される窒素含有複素環基は、ピリジル基、ピラジニル基、ピリミジニル基、ピリダジニル基、トリアゾリル基、キノリル基、イソキノリル基、及びベンゾイミダゾリル基からなる群より選択される少なくとも一種である、項１又は２に記載のゴム組成物。
項４．
前記式（１）においてＹで示されるアリーレン基及び式（１ｂ）におけるＹ´で示されるアリーレン基がフェニレン基又はナフチレン基であり、前記アリーレン基はさらに置換基を有していてもよい、項１～３の何れかに記載のゴム組成物。
項５．
前記成分（ｃ）が下記式（２ａ）で表される化合物である、項１～４の何れかに記載のゴム組成物。

〔式中、Ｚ´は炭素数６～２５のアルキル基であり、Ａ´は式（ia）又は（iia）であり、Ｒ^８、Ｒ^９、Ｒ^１０及びＲ^１１は、各々水素原子又は炭素数１～６のアルキル基を示す。〕
項６．
前記ゴム成分はジエン系ゴムである、項１～５の何れかに記載のゴム組成物。
項７．
さらに、成分（ｄ）シリカを含む、項１～６の何れかに記載のゴム組成物。
項８．
項１～７の何れかに記載のゴム組成物を用いて作製されたタイヤ。
項９．
下記成分（ｂ）及び（ｃ）を含むゴム用添加剤。
成分（ｂ）；下記式（１）で表される化合物
成分（ｃ）；下記式（２）で表される化合物

〔式中、Ａは下記式（i）又は（ii）で示される基を示す。
式（i）又は（ii）において、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、各々水素原子又は炭素数１～１８のアルキル基を示す。
Ｘは、窒素含有複素環基、炭素数１～５のアルキル基、アリール基、又は基－Ｙ－ＣＯ－ＮＨＡを示す。或いは、Ｘは、基－ＣＨＲ^６－ＣＲ^５＝Ｎ－を介してＡと結合することにより環を形成してもよい。これら各基及び環は、さらに置換基を有していてもよい。
Ｙは、２価の窒素含有複素環基、炭素数１～１８のアルキレン基、又はアリーレン基を示す。
Ｒ^５は、水素原子、炭素数１～１８のアルキル基、又はアリール基を、
Ｒ^６は、水素原子、ハロゲン原子、アルキル基、アルケニル基、ヒドラジド基、アミノ基、チオカルボキシル基、又はチオール基を示し、これら各基は更に置換基を有していてもよい。
Ｚは、炭素数６～４０のアルキル基を示し、該アルキル基はさらに置換基を有していてもよい。〕

That is, the present invention provides the following rubber compositions, tires, and rubber additives.
Item 1.
A rubber composition containing the following components (a), (b) and (c).
Component (a); Rubber component component (b); Compound represented by the following formula (1) Component (c); Compound represented by the following formula (2)

[In the formula, A represents a group represented by the following formula (i) or (ii).
In formula (i) or (ii), R ¹ , R ² , R ³ and R ⁴ represent hydrogen atoms or alkyl groups having 1 to 18 carbon atoms, respectively.
X represents a nitrogen-containing heterocyclic group, an alkyl group having 1 to 5 carbon atoms, an aryl group, or a group-Y-CO-NHA. Alternatively, X may form a ring by binding to A via the group -CHR ⁶ -CR ⁵ = N-. Each of these groups and rings may further have a substituent.
Y represents a divalent nitrogen-containing heterocyclic group, an alkylene group having 1 to 18 carbon atoms, or an arylene group.
R5 has a hydrogen atom, an alkyl group having ¹ to 18 carbon atoms, or an aryl group.
R ⁶ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydrazide group, an amino group, a thiocarboxyl group, or a thiol group, and each of these groups may further have a substituent.
Z represents an alkyl group having 6 to 40 carbon atoms, and the alkyl group may further have a substituent. ]

Item 2.
The rubber according to claim 1, wherein the compound represented by the formula (1) is at least one selected from the group consisting of the compounds represented by the following formulas (1a), (1b), and (1c). Composition.

[In the formula, X'represents a nitrogen-containing heterocyclic group, an alkyl group having 1 to 5 carbon atoms, or an aryl group.
Y'represents a divalent nitrogen-containing heterocyclic group, an alkylene group having 1 to 18 carbon atoms, or an arylene group.
Each group represented by X'and Y'may further have a substituent.
A, R ⁵ and R ⁶ are the same as described above. ]
Item 3.
The nitrogen-containing heterocyclic group represented by X in the formula (1) and the nitrogen-containing heterocyclic group represented by X'in the formula (1a) are a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridadinyl group, a triazolyl group and a quinolyl group. Item 3. The rubber composition according to Item 1 or 2, which is at least one selected from the group consisting of an isoquinolyl group and a benzoimidazolyl group.
Item 4.
The arylene group represented by Y in the formula (1) and the arylene group represented by Y'in the formula (1b) may be a phenylene group or a naphthylene group, and the arylene group may further have a substituent. The rubber composition according to any one of 1 to 3.
Item 5.
Item 6. The rubber composition according to any one of Items 1 to 4, wherein the component (c) is a compound represented by the following formula (2a).

[In the formula, Z'is an alkyl group having 6 to 25 carbon atoms, A'is a formula (ia) or (iia), and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are hydrogen atoms or carbons, respectively. The number 1 to 6 alkyl groups are shown. ]
Item 6.
Item 6. The rubber composition according to any one of Items 1 to 5, wherein the rubber component is a diene-based rubber.
Item 7.
Item 6. The rubber composition according to any one of Items 1 to 6, further comprising the component (d) silica.
Item 8.
A tire manufactured by using the rubber composition according to any one of Items 1 to 7.
Item 9.
An additive for rubber containing the following components (b) and (c).
Component (b); Compound represented by the following formula (1) Component (c); Compound represented by the following formula (2)

[In the formula, A represents a group represented by the following formula (i) or (ii).
In formula (i) or (ii), R ¹ , R ² , R ³ and R ⁴ represent hydrogen atoms or alkyl groups having 1 to 18 carbon atoms, respectively.
X represents a nitrogen-containing heterocyclic group, an alkyl group having 1 to 5 carbon atoms, an aryl group, or a group-Y-CO-NHA. Alternatively, X may form a ring by binding to A via the group -CHR ⁶ -CR ⁵ = N-. Each of these groups and rings may further have a substituent.
Y represents a divalent nitrogen-containing heterocyclic group, an alkylene group having 1 to 18 carbon atoms, or an arylene group.
R5 has a hydrogen atom, an alkyl group having ¹ to 18 carbon atoms, or an aryl group.
R ⁶ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydrazide group, an amino group, a thiocarboxyl group, or a thiol group, and each of these groups may further have a substituent.
Z represents an alkyl group having 6 to 40 carbon atoms, and the alkyl group may further have a substituent. ]

The rubber composition of the present invention has sufficiently low heat generation properties and at the same time has excellent processability.

(1. Rubber composition)
The rubber composition of the present invention contains the following components (a), (b), and (c).
Component (a); Rubber component Component (b); Compound represented by the following formula (1) Component (c); Compound represented by the following formula (2)

〔式中、Ａは下記式（i）又は（ii）で示される基を示す。
式（i）又は（ii）において、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、各々水素原子又は炭素数１～１８のアルキル基を示す。
Ｘは、窒素含有複素環基、炭素数１～５のアルキル基、アリール基、又は基－Ｙ－ＣＯ－ＮＨＡを示す。或いは、Ｘは、基－ＣＨＲ^６－ＣＲ^５＝Ｎ－を介してＡと結合することにより環を形成してもよい。これら各基及び環は、さらに置換基を有していてもよい。
Ｙは、２価の窒素含有複素環基、炭素数１～１８のアルキレン基、又はアリーレン基を示す。
Ｒ^５は、水素原子、炭素数１～１８のアルキル基、又はアリール基を、
Ｒ^６は、水素原子、ハロゲン原子、アルキル基、アルケニル基、ヒドラジド基、アミノ基、チオカルボキシル基、又はチオール基を示し、これら各基は更に置換基を有していてもよい。
Ｚは、炭素数６～４０のアルキル基を示し、該アルキル基はさらに置換基を有していてもよい。〕

[In the formula, A represents a group represented by the following formula (i) or (ii).
In formula (i) or (ii), R ¹ , R ² , R ³ and R ⁴ represent hydrogen atoms or alkyl groups having 1 to 18 carbon atoms, respectively.
X represents a nitrogen-containing heterocyclic group, an alkyl group having 1 to 5 carbon atoms, an aryl group, or a group-Y-CO-NHA. Alternatively, X may form a ring by binding to A via the group -CHR ⁶ -CR ⁵ = N-. Each of these groups and rings may further have a substituent.
Y represents a divalent nitrogen-containing heterocyclic group, an alkylene group having 1 to 18 carbon atoms, or an arylene group.
R5 has a hydrogen atom, an alkyl group having ¹ to 18 carbon atoms, or an aryl group.
R ⁶ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydrazide group, an amino group, a thiocarboxyl group, or a thiol group, and each of these groups may further have a substituent.
Z represents an alkyl group having 6 to 40 carbon atoms, and the alkyl group may further have a substituent. ]

(1.1. Component (a); Rubber component)
The rubber component contained in the rubber composition of the present invention is not particularly limited, and both a diene-based rubber and a non-diene-based rubber can be preferably used. Here, examples of the diene-based rubber include, and are not limited to, natural rubber (NR), synthetic diene-based rubber, and a mixture of natural rubber and synthetic diene-based rubber.

Natural rubber includes natural rubber latex, technically rated rubber (TSR), smoked sheet (RSS), backlash, natural rubber derived from Tochu, natural rubber derived from Guayur, natural rubber derived from Russian dandelion, and epoxidation. Examples thereof include modified natural rubber such as natural rubber, methacrylic acid-modified natural rubber, and styrene-modified natural rubber.

Examples of synthetic diene-based rubbers include styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), nitrile rubber (NBR), chloroprene rubber (CR), and ethylene-propylene-diene ternary products. Examples thereof include polymer rubber (EPDM), styrene-isoprene-styrene ternary block copolymer (SIS), styrene-butadiene-styrene ternary block copolymer (SBS), and modified synthetic diene-based rubbers thereof. Examples of the modified synthetic diene-based rubber include diene-based rubbers produced by modification methods such as main chain modification, single-ended modification, and double-ended modification. Here, examples of the modified functional group of the modified synthetic diene rubber include those containing at least one functional group containing a heteroatom such as an epoxy group, an amino group, an alkoxy group, and a hydroxyl group. Further, the ratio of cis / trans / vinyl in the diene portion is not particularly limited, and any ratio can be preferably used. Further, the average molecular weight and the molecular weight distribution of the diene rubber are not particularly limited, and an average molecular weight of 5 to 3 million can be preferably used. The method for producing the synthetic diene rubber is also not particularly limited, and examples thereof include those synthesized by emulsion polymerization, solution polymerization, radical polymerization, anionic polymerization, cationic polymerization and the like.

As the non-diene rubber, known rubbers can be widely used.

The rubber component preferably contains a diene-based rubber, preferably contains 50 parts by mass or more of the diene-based rubber, more preferably 75 parts by mass or more, and 80 to 100 parts by mass, out of 100 parts by mass of the rubber component. It is particularly preferable that it is contained in parts by mass.

Further, regarding the glass transition point of the diene rubber, those in the range of −70 ° C. to −20 ° C. are effective from the viewpoint of achieving both wear resistance and braking characteristics. The rubber composition of the present invention is preferably a diene-based rubber in which 50% by mass or more of the diene-based rubber has a glass transition point in the range of −70 ° C. to −20 ° C.

The rubber component can be used alone or in combination of two or more. Among them, the preferable rubber component is natural rubber, IR, SBR, BR or a mixture of two or more kinds selected from these, and more preferably natural rubber, SBR, BR or a mixture of two or more kinds selected from these. .. The blending ratio thereof is not particularly limited, but it is preferable to mix natural rubber, SBR, BR or a mixture thereof in 100 parts by mass of the rubber component in a ratio of 50 to 100 parts by mass, preferably 75 to 100 parts. It is more preferable to mix by mass. When blending a mixture of SBR and BR, the total amount of SBR and BR is preferably in the above range. Further, the SBR at this time is 50 to 100 parts by mass, and the BR is preferably in the range of 0 to 50 parts by mass.

(1.2. Component (b); compound represented by formula (1))
The component (b) is a compound represented by the following formula (1).

〔式中、Ａは下記式（i）又は（ii）で示される基を示す。
式（i）又は（ii）において、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、各々水素原子又は炭素数１～１８のアルキル基を示す。
Ｘは、窒素含有複素環基、炭素数１～５のアルキル基、アリール基、又は基－Ｙ－ＣＯ－ＮＨＡを示す。或いは、Ｘは、基－ＣＨＲ^６－ＣＲ^５＝Ｎ－を介してＡと結合することにより環を形成してもよい。これら各基及び環は、さらに置換基を有していてもよい。
Ｙは、２価の窒素含有複素環基、炭素数１～１８のアルキレン基、又はアリーレン基を示す。
Ｒ^５は、水素原子、炭素数１～１８のアルキル基、又はアリール基を、
Ｒ^６は、水素原子、ハロゲン原子、アルキル基、アルケニル基、ヒドラジド基、アミノ基、チオカルボキシル基、又はチオール基を示し、これら各基は更に置換基を有していてもよい。〕

[In the formula, A represents a group represented by the following formula (i) or (ii).
In formula (i) or (ii), R ¹ , R ² , R ³ and R ⁴ represent hydrogen atoms or alkyl groups having 1 to 18 carbon atoms, respectively.
X represents a nitrogen-containing heterocyclic group, an alkyl group having 1 to 5 carbon atoms, an aryl group, or a group-Y-CO-NHA. Alternatively, X may form a ring by binding to A via the group -CHR ⁶ -CR ⁵ = N-. Each of these groups and rings may further have a substituent.
Y represents a divalent nitrogen-containing heterocyclic group, an alkylene group having 1 to 18 carbon atoms, or an arylene group.
R5 has a hydrogen atom, an alkyl group having ¹ to 18 carbon atoms, or an aryl group.
R ⁶ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydrazide group, an amino group, a thiocarboxyl group, or a thiol group, and each of these groups may further have a substituent. ]

In the formula (1), the group represented by A represents the group represented by the formula (i) or (ii). In formula (i) or (ii), R ¹ , R ² , R ³ and R ⁴ represent hydrogen atoms or alkyl groups having 1 to 18 carbon atoms, respectively.

The "alkyl group having 1 to 18 carbon atoms" is not particularly limited, and examples thereof include linear, branched, and cyclic alkyl groups, and specific examples thereof include methyl, ethyl, and n-. Linear or branched alkyl groups with 1 to 4 carbon atoms such as propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, and 1-ethylpropyl, n-pentyl, isopentyl, neopentyl. , N-hexyl, isohexyl, 3-methylpentyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, 5-propylnonyl, n-tridecyl, n-tetradecyl, n -A linear or branched alkyl group having 5 to 18 carbon atoms to which pentadecyl, hexadecyl, heptadecyl, octadecyl and the like are added; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like having 3 to 8 carbon atoms. Cyclic alkyl groups and the like can be mentioned.

Among them, as the group represented by A, R ¹ and R ² are preferably hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, and R ³ and R ⁴ are preferably hydrogen atoms or alkyl groups having 1 to 18 carbon atoms. R ¹ and R ² are hydrogen atoms, R ³ and R ⁴ are more preferably alkyl groups having 1 to 12 carbon atoms, R ¹ and R ² are hydrogen atoms, and R ³ and R ⁴ are alkyl groups having 1 to 6 carbon atoms. Is particularly preferable.

The compound represented by the above formula (1) is preferably at least one selected from the group consisting of the compounds represented by the following formulas (1a), (1b) and (1c).

〔式中、Ｘ´は窒素含有複素環基、炭素数１～５のアルキル基、又はアリール基を示す。
Ｙ´は２価の窒素含有複素環基、炭素数１～１８のアルキレン基、又はアリーレン基を示す。
Ｘ´及びＹ´で示される各基は、さらに置換基を有していてもよい。
Ａ、Ｒ^５、及びＲ^６は前記に同じである。〕

[In the formula, X'represents a nitrogen-containing heterocyclic group, an alkyl group having 1 to 5 carbon atoms, or an aryl group.
Y'represents a divalent nitrogen-containing heterocyclic group, an alkylene group having 1 to 18 carbon atoms, or an arylene group.
Each group represented by X'and Y'may further have a substituent.
A, R ⁵ and R ⁶ are the same as described above. ]

Next, the compound represented by the formula (1a) will be described.

〔式中、Ｘ´は窒素含有複素環基、炭素数１～５のアルキル基、又はアリール基を示す。Ａは下記式（i）又は（ii）で示される基を示す。〕

[In the formula, X'represents a nitrogen-containing heterocyclic group, an alkyl group having 1 to 5 carbon atoms, or an aryl group. A represents a group represented by the following formula (i) or (ii). ]

〔式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、各々水素原子又は炭素数１～１８のアルキル基を示す。〕

[In the formula, R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. ]

In X'in the formula (1a), the "nitrogen-containing heterocyclic group" is not particularly limited, and for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazinyl, 2-pyrimidyl, 4-pyrimidyl, 5-. Pyrimidil, 3-pyridadyl, 4-pyridadyl, 4- (1,2,3-triazil), 5- (1,2,3-triazil), 2- (1,3,5-triazil), 3- (1) , 2,4-Triazil), 5- (1,2,4-Triazil), 6- (1,2,4-Triazil), 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6- Kinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalyl, 3-quinoxalyl, 5-quinoxalyl, 6-quinoxalyl, 7-quinoxalyl, 8-quinoxalyl, 3-cinnolyl, 4-cinnolyl, 5-cinnolyl, 6-cinnolyl, 7-cinnolyl, 8-cinnolyl, 2-quinazolyl, 4-quinazolyl, 5-quinazolyl, 6- Kinazolyl, 7-quinazolyl, 8-kinazolyl, 1-tetrahydroquinolyl, 2-tetrahydroquinolyl, 3-tetrahydroquinolyl, 4-tetrahydroquinolyl, 5-tetrahydroquinolyl, 6-tetrahydroquinolyl, 7-tetrahydroquinolyl Lil, 8-tetrahydroquinoline, 1-pyrrolill, 2-pyrrolill, 3-pyrrolill, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5- Pyrazolyl, 1- (1,2,3-triazolyl), 4- (1,2,3-triazolyl), 5- (1,2,3-triazolyl), 1- (1,2,4-triazolyl), 3- (1,2,4-triazolyl), 5- (1,2,4-triazolyl), 1-tetrazolyl, 5-tetrazolyl, 1-indrill, 2-indrill, 3-indrill, 4-indrill, 5- Indrill, 6-Indrill, 7-Indrill, 1-Isoindrill, 2-Isoindrill, 3-Isoindrill, 4-Isoindrill, 5-Isoindrill, 6-Isoindrill, 7-Isoindryl, 1-benzoimidazolyl, 2-benzoimidazolyl, 4-benzoimidazolyl, 5-benzoimidazolyl, 6-benzoimidazolyl, 7-benzoimidazolyl, 1-indazolyl, 3-indazolyl, 4-inda Zoryl, 5-indazolyl, 6-indazolyl, 7-indazolyl, 1-piperazyl, 2-piperazil, 1-piperidyl, 2-piperidyl, 3-piperidyl, 4-piperidyl, 1-pyrrolidyl, 2-pyrrolidyl, 3-pyrrolidyl, etc. Can be mentioned. Among these, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridadinyl group, a triazolyl group, a quinolyl group, an isoquinolyl group, or a benzoimidazolyl group is preferable.

In X'in the above formula (1a), the "alkyl group having 1 to 5 carbon atoms" is not particularly limited, and examples thereof include linear, branched or cyclic alkyl groups having 1 to 5 carbon atoms. Specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 1-ethylpropyl, n-pentyl, isopentyl, neopentyl, cyclopropyl, cyclobutyl. , Cyclopentyl and the like. Among these, an alkyl group having 1 to 3 carbon atoms is preferable.

In X'in the above formula (1a), the "aryl group" is not particularly limited, and examples thereof include a phenyl group and a naphthyl group. Among these, it is preferably a phenyl group.

X'may further have a substituent. The substituent is not particularly limited, and examples thereof include an amino group, a hydroxyl group, a thiol group, an alkyl group, a thioalkyl group, an alkoxy group, a halogen atom, a heterocyclic group, and a nitro group.

The "amino group" as a substituent further possessed by X'is not only the amino group represented by -NH ₂ , but also, for example, methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino and isobutyl. Amino, s-butylamino, t-butylamino, 1-ethylpropylamino, n-pentylamino, neopentylamino, n-hexylamino, isohexylamino, 3-methylpentylamino group, etc. having 1 to 6 carbon atoms. Linear or branched monoalkylamino group; Substitution of dialkylamino group having two linear or branched alkyl groups having 1 to 6 carbon atoms such as dimethylamino, ethylmethylamino, diethylamino group, etc. It is defined as including an amino group.

The "alkyl group" as the substituent further possessed by X'is not particularly limited, and examples thereof include linear, branched or cyclic alkyl groups, and specific examples thereof include methyl, ethyl and n. -A linear or branched alkyl group having 1 to 4 carbon atoms such as propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, and 1-ethylpropyl, n-pentyl, isopentyl, Neopentyl, n-hexyl, isohexyl, 3-methylpentyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, 5-propylnonyl, n-tridecyl, n-tetradecyl, Linear or branched alkyl group having 5 to 18 carbon atoms including n-pentadecyl, hexadecyl, heptadecyl, octadecyl and the like; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like having 3 to 8 carbon atoms. Cyclic alkyl group and the like.

The "thioalkyl group" as the substituent further possessed by X'is not particularly limited, and examples thereof include a linear or branched thioalkyl group, and specific examples thereof include a methylthio group and an ethylthio group. n-propiothio group, isopropiothio group, n-butylthio group, isobutylthio group, t-butylthio group, 1-ethylpropylthio group, n-pentylthio group, isopentylthio group, neopentylthio group, n-hexylthio group. , Isohexylthio group, 3-methylpentylthio group, n-heptylthio group, n-octylthio group, n-nonylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, 5-propylnonylthio group, Examples thereof include an n-tridecylthio group, an n-tetradecylthio group, an n-pentadecylthio group, a hexadecylthio group, a heptadecylthio group, an octadecylthio group and the like.

The "alkoxy group" as the substituent further possessed by X'is not particularly limited, and examples thereof include linear, branched or cyclic alkoxy groups, and specific examples thereof include methoxy, ethoxy, and n. -Linear or branched alkoxy groups of propoxy, isopropoxy, n-butoxy, t-butoxy, n-pentyloxy, neopentyloxy, n-hexyloxy groups; cyclopropyloxy, cyclobutyloxy, cyclopentyloxy , Cyclic alkoxy groups such as cyclohexyloxy, cycloheptyloxy, cyclooctyloxy group and the like.

Examples of the "halogen atom" as a substituent further possessed by X'include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The "heterocyclic group" as a substituent further possessed by X'is not particularly limited, and is, for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazinyl, 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl. , 3-Pyridazil, 4-Pyridadyl, 4- (1,2,3-Triazil), 5- (1,2,3-Triazil), 2- (1,3,5-Triazil), 3- (1, 2,4-Triazil), 5- (1,2,4-Triazil), 6- (1,2,4-Triazil), 2-quinoline, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl , 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalyl, 3-quinoxalyl, 5-quinoxalyl, 6 -Kinoxalyl, 7-Kinoxalyl, 8-Kinoxalyl, 3-Synolyl, 4-Synolyl, 5-Synolyl, 6-Synolyl, 7-Synolyl, 8-Synoryl, 2-Kinazolyl, 4-Kynazolyl, 5-Kynazolyl, 6-Kynazolyl , 7-quinazolyl, 8-quinazolyl, 1-phthalazyl, 4-phthalazyl, 5-phthalazyl, 6-phthalazyl, 7-phthalazyl, 8-phthalazyl, 1-tetrahydroquinolyl, 2-tetrahydroquinolyl, 3-tetrahydroquinolyl , 4-Tetrahydroquinoline, 5-Tetrahydroquinoline, 6-Tetrahydroquinoline, 7-Tetrahydroquinoline, 8-Tetrahydroquinoline, 1-Pyrrolyl, 2-Pyrrolyl, 3-Pyrrolyl, 2-Frill, 3-Frill , 2-thienyl, 3-thienyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5 -Oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 4- (1,2,3-thiazolyzolyl) , 5- (1,2,3-thiadiazolyl), 3- (1,2,5-thiadiazolyl), 2- (1,3,4-thiadiazolyl), 4- (1,2,3-oxadiazolyl), 5 -(1,2,3-oxadiazolyl), 3- (1,2,4-oxadiazolyl), 5- (1,2,4-oxadiazolyl), 3- (1,2,5) -Oxadiazolyl), 2- (1,3,4-oxadiazolyl), 1- (1,2,3-triazolyl), 4- (1,2,3-triazolyl), 5- (1,2,3-triazolyl) ), 1- (1,2,4-triazolyl), 3- (1,2,4-triazolyl), 5- (1,2,4-triazolyl), 1-tetrazolyl, 5-tetrazolyl, 1-indrill, 2-Indrill, 3-Indrill, 4-Indrill, 5-Indrill, 6-Indrill, 7-Indrill, 1-isoindrill, 2-isoindrill, 3-isoindrill, 4-isoindrill, 5-isoindrill, 6-isoindrill, 7- Isoindrill, 1-benzoimidazolyl, 2-benzoimidazolyl, 4-benzoimidazolyl, 5-benzoimidazolyl, 6-benzoimidazolyl, 7-benzoimidazolyl, 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, 7-benzofuranyl, 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofunyl, 2-benzothienyl, 3-benzothienyl, 4 -Benzothienyl, 5-benzothienyl, 6-benzothienyl, 7-benzothienyl, 2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzo Oxazolyl, 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl, 1-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl, 2- Morphoryl, 3-morpholyl, 4-morpholyl, 1-piperidyl, 2-piperazyl, 1-piperidyl, 2-piperidyl, 3-piperidyl, 4-piperidyl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyrani Le, 2-tetrahydrothiopyranyl, 3-tetrahydrothiopyranyl, 4-tetrahydrothiopyranyl, 1-pyrrolidyl, 2-pyrrolidyl, 3-pyrrolidyl, furanyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydro Examples thereof include thienyl, 3-tetrahydrothienyl, 5-methyl-3-oxo-2,3-dihydro-1H-pyrazole-4-yl group and the like.

Among the compounds represented by the formula (1a), X'is a nitrogen-containing heterocyclic group, an alkyl group having 1 to 3 carbon atoms, and R ¹ and R ² of A are hydrogen atoms, R ³ and R ⁴ . Is preferably an alkyl group having 1 to 18 carbon atoms, and X'is a pyridyl group, a triazolyl group, a pyrazil group, an isoquinolyl group, a pyrimidyl group, a pyridadyl group, a benzoimidazolyl group, and an alkyl group having 1 to 3 carbon atoms. Further, it is more preferable that R ¹ and R ² of A are hydrogen atoms, R ³ and R ⁴ are alkyl groups having 1 to 12 carbon atoms, X'is a pyridyl group or a triazolyl group, and R of A is. It is particularly preferable that ¹ and R ² are hydrogen atoms, and R ³ and R ⁴ are alkyl groups having 1 to 6 carbon atoms.

More specifically, the compound represented by the formula (1a) includes pyridine-2-carbohydrazide, pyridine-3-carbohydrazide, 4H-1,2,4-triazole-3-carbohydrazide, and pyrazine-2-. Carbohydrazide, Isoquinoline-1-Carbohydrazide, Pyrimidin-2-Carbohydrazide, Pyridadin-3-Carbohydrazide, Pyridadin-4-Carbohydrazide, 2- (1H-benzo [d] imidazole-1-yl) acetohydrazide, 2 -Amino-4- (methylsulfanyl) butanehydrazide, 2-amino-3- (dodecylsulfanyl) propanehydrazide, N'-(4-methylpentane-2-iriden) pyridine-2-carbohydrazide, N'-(propane) -2-Ilidene) pyridine-2-carbohydrazide and N'-(tridecane-2-iriden) pyridine-2-carbohydrazide can be exemplified. Among them, pyridine-2-carbohydrazide, pyridine-3-carbohydrazide, 4H-1,2,4-triazole-3-carbohydrazide, N'-(4-methylpentane-2-iriden) pyridine-2-carbohydrazide. , N'-(tridecane-2-iriden) pyridin-2-carbohydrazide is preferred.

Y'in the formula (1b) represents a divalent nitrogen-containing heterocyclic group, an alkylene group having 1 to 18 carbon atoms, or an arylene group.

〔式中、Ｙ´は２価の窒素含有複素環基、炭素数１～１８のアルキレン基、又はアリーレン基を示す。Ｙ´で示される各基は、さらに置換基を有していてもよい。Ａは下記式（i）又は（ii）で示される基を示す。〕

[In the formula, Y'represents a divalent nitrogen-containing heterocyclic group, an alkylene group having 1 to 18 carbon atoms, or an arylene group. Each group represented by Y'may further have a substituent. A represents a group represented by the following formula (i) or (ii). ]

〔式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、各々水素原子又は炭素数１～１８のアルキル基を示す。〕

[In the formula, R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. ]

When Y'is a divalent nitrogen-containing heterocyclic group, each of these groups is preferably a pyridylene group, a pyrimidirene group, a pyrazinylene group, a pyridadinylene group or a triazilene group.

When Y'is an alkylene group, specific examples thereof include linear, branched or cyclic alkylene groups, and specific examples thereof include methylene, ethylene, n-propylene, isopropylene and n-butylene. , Isobutylene, s-butylene, t-butylene, 1-ethylpropylene, n-pentylene, isopentylene, neopentylene, n-hexylene, isohexylene, 3-methylpentylene, n-heptylene, n-octylene, n-nonylene, n- Decylene, n-undecylene, n-dodecylene, 5-propylnonylene, n-tridecylene, n-tetradecylene, n-pentadecylene, hexadecylene, heptadecylene, octadecylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptyrene, cyclo Examples include octylene.

When Y'is an arylene group, specifically, it is preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group.

Y'may further have a substituent. The substituent is the same as X'.

The group represented by A in the compound represented by the formula (1b) is preferably a group represented by the formula (i), and it is particularly preferable that R ¹ and R ² are hydrogen atoms.

Among the compounds represented by the above formula (1b), Y'is a divalent nitrogen-containing heterocyclic group, an alkylene group having 1 to 18 carbon atoms, or an arylene group, and R ¹ and R ² of A are The hydrogen atom, R ³ and R ⁴ are preferably an alkyl group having 1 to 18 carbon atoms, Y'is a pyridylene group, an alkylene group having 1 to 18 carbon atoms, a phenylene group, a naphthylene group, and R of A. It is more preferable that ¹ and R ² are hydrogen atoms, R ³ and R ⁴ are alkyl groups having 1 to 12 carbon atoms, Y'is a pyridylene group or a phenylene group, and A is represented by the formula (i). It is particularly preferable that R ¹ and R ² are hydrogen atoms.

More specifically, the compound represented by the above formula (1b) is pyridine-3,5-dicarbohydrazide, pyridine-2,6-dicarbohydrazide, pyridine-2,4-dicarbohydrazide, pyridine-. Examples thereof include 2,5-dicarbohydrazide, benzene-1,3-dicarbohydrazide, and among them, pyridine-3,5-dicarbohydrazide and benzene-1,3-dicarbohydrazide are preferable.

Next, the compound represented by the formula (1c) will be described.

〔式中、Ｒ^５は、水素原子、炭素数１～１８のアルキル基、又はアリール基を、
Ｒ^６は、水素原子、ハロゲン原子、アルキル基、アルケニル基、ヒドラジド基、アミノ基、チオカルボキシル基、又はチオール基を示し、これら各基は更に置換基を有していてもよい。〕

[ ^In the formula, R5 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group.
R ⁶ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydrazide group, an amino group, a thiocarboxyl group, or a thiol group, and each of these groups may further have a substituent. ]

^In R5 in the above formula (1c), the "alkyl group having 1 to 18 carbon atoms" is not particularly limited, and examples thereof include linear, branched, and cyclic alkyl groups, and specific examples thereof. , For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 1-ethylpropyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl. , N-Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, 5-propylnonyl, n-tridecyl, n-tetradecyl, n-pentadecyl, hexadecyl, heptadecyl, octadecyl, cyclopropyl , Cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. Among them, R5 is preferably methyl, ethyl, n ^- propyl, n-butyl, and more preferably methyl.

^In R5 in the above formula (1c), the "aryl group" is not particularly limited, and examples thereof include a phenyl group and a naphthyl group.

In R ⁶ in the above formula (1c), the "halogen atom" is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In R ⁶ in the above formula (1c), the "alkyl group" is not particularly limited, and examples thereof include linear, branched or cyclic alkyl groups, and specific examples thereof include methyl and ethyl. , N-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl and other linear or branched alkyl groups having 1 to 4 carbon atoms, as well as 1-ethylpropyl, n-pentyl, Isopentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, 5-propylnonyl, n-tridecyl, n- Linear or branched alkyl group having 5 to 18 carbon atoms including tetradecyl, n-pentadecyl, hexadecyl, heptadecyl, octadecyl and the like; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like having 3 carbon atoms. 8 to 8 cyclic alkyl groups and the like can be mentioned.

In R ⁶ in the above formula (1c), the "alkenyl group" is not particularly limited, and examples thereof include a vinyl group and an allyl group.

In R ⁶ in the above formula (1c), the "amino group" is not only an amino group represented by -NH ₂ , but also, for example, methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino. , Isobutylamino, s-butylamino, t-butylamino, 1-ethylpropylamino, n-pentylamino, neopentylamino, n-hexylamino, isohexylamino, 3-methylpentylamino group, etc. 6 linear or branched monoalkylamino group; dialkylamino group having 2 linear or branched alkyl groups having 1 to 6 carbon atoms such as dimethylamino, ethylmethylamino, diethylamino group, etc. It is defined that the substituted amino group of is also included.

In R ⁶ in the above formula (1c), a hydrogen atom, a hydrazide group, and a thiol group are preferable, and a hydrogen atom is more preferable.

R ⁶ may further have a substituent. The substituent is the same as X'.

More specifically, the compounds represented by the formula (1c) include 3-methyl-5-pyrazolone, 3-phenyl-5-pyrazolone, and 2- (3-methyl-5-oxo-4,5-dihydro). -1H-pyrazole-4-yl) acetohydrazide can be mentioned. Of these, 3-methyl-5-pyrazolone is preferable.

In the rubber composition of the present invention, the compound represented by the formula (1) may contain only one kind selected from the above-mentioned compounds alone, or may contain two or more kinds in a mixture. good.

The compounding ratio of the compound represented by the formula (1) is preferably 0.01 to 30 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the rubber component of the component (a). Is more preferable. By blending in the ratio, the effect of improving low heat generation can be effectively obtained.

(1.3. Component (c); compound represented by formula (2))
The component (c) is a compound represented by the following formula (2).

〔式中、Ａは下記（i）又は（ii）で示される基を示す。
式（i）又は（ii）において、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、各々水素原子又は炭素数１～１８のアルキル基を示す。
Ｚは、炭素数６～４０のアルキル基を示し、該アルキル基はさらに置換基を有していてもよい。〕

[In the formula, A indicates the group represented by the following (i) or (ii).
In formula (i) or (ii), R ¹ , R ² , R ³ and R ⁴ represent hydrogen atoms or alkyl groups having 1 to 18 carbon atoms, respectively.
Z represents an alkyl group having 6 to 40 carbon atoms, and the alkyl group may further have a substituent. ]

Z in the above formula (2) may have 6 or more carbon atoms, and may indicate, for example, an alkyl group having 6 to 40 carbon atoms and may further have a substituent. The number of carbon atoms of the alkyl group is preferably 8 to 35, more preferably 10 to 30, and even more preferably 12 to 25. Even when the number of carbon atoms is larger than 40, the expected increase in the effect cannot be obtained.

Further, the alkyl group constituting Z may have a substituent, and the substituents include an amino group, a hydroxyl group, a thiol group, an alkyl group, a thioalkyl group, an alkoxy group, a halogen atom, a heterocyclic group, and a substituent. At least one selected from the group consisting of nitro groups can be mentioned.

In Z in the above formula (2), the "alkyl group having 6 to 40 carbon atoms" is not particularly limited, and examples thereof include linear, branched or cyclic alkyl groups having 6 to 40 carbon atoms. Specifically, for example, n-hexyl, isohexyl, 3-methylpentyl, cyclopentylmethyl, n-heptyl, isoheptyl, neopentyl, 2-ethylpentyl, n-octyl, isooctyl, neooctyl, cyclooctyl, n-nonyl, Isononyl, neononyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-hexylnonyl, n-heptadecyl, n-octadecyl, n-nonadecil, icosyl. , Eikosyl, Hen Eikosyl, Docosyl, Tricosyl, Tetracosyl, Pentacosyl, Hexacosyl, Heptakosyl, Octacosyl, Nonacosyl, Triacocyl, Hentriacontyl, Dotriacyl, Tritriacontyl, Tetratoriacontyl, Pentriacontyl, Hexatriacontyl, Tetracontyl, 2-Hexadecyl heptadecyl and the like can be mentioned.

The "amino group" of the substituent of Z in the above formula (2) is not only the amino group represented by -NH ₂ , but also, for example, methylamino, ethylamino, n-propylamino, isopropylamino, n. -Carbons such as butylamino, isobutylamino, s-butylamino, t-butylamino, 1-ethylpropylamino, n-pentylamino, neopentylamino, n-hexylamino, isohexylamino, 3-methylpentylamino group Linear or branched monoalkylamino group of number 1 to 6; Dialkyl having two linear or branched alkyl groups of 1 to 6 carbon atoms such as dimethylamino, ethylmethylamino, diethylamino group, etc. It is defined as including a substituted amino group such as an amino group.

The "alkyl group" of the substituent of Z in the above formula (2) is not particularly limited, and examples thereof include linear, branched, and cyclic alkyl groups, and specific examples thereof include, for example. Linear or branched alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, and 1-ethylpropyl, n. -Pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undesyl, n-dodecyl, 5-propylnonyl, n-tridecyl , N-tetradecyl, n-pentadecyl, hexadecyl, heptadecyl, octadecyl, etc., and a linear or branched alkyl group having 5 to 18 carbon atoms; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. Examples thereof include a cyclic alkyl group having 3 to 8 carbon atoms.

The "thioalkyl group" of the substituent of Z in the above formula (2) is not particularly limited, and examples thereof include a linear or branched thioalkyl group, and specific examples thereof include methylthio. Group, ethylthio group, n-propiothio group, isopropiothio group, n-butylthio group, isobutylthio group, t-butylthio group, 1-ethylpropylthio group, n-pentylthio group, isopentylthio group, neopentylthio group , N-hexylthio group, isohexylthio group, 3-methylpentylthio group, n-heptylthio group, n-octylthio group, n-nonylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, 5- Examples thereof include a propylnonylthio group, an n-tridecylthio group, an n-tetradecylthio group, an n-pentadecylthio group, a hexadecylthio group, a heptadecylthio group, an octadecylthio group and the like.

The "alkoxy group" of the substituent of Z in the above formula (2) is not particularly limited, and examples thereof include linear, branched and cyclic alkoxy groups, and specific examples thereof include, for example. Linear or branched alkoxy groups of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, n-pentyloxy, neopentyloxy, n-hexyloxy groups; cyclopropyloxy, cyclo Examples thereof include cyclic alkoxy groups such as butyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy groups.

Similarly, in Z in the above formula (2), examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Similarly, the "heterocyclic group" of the substituent of Z in the above formula (2) is not particularly limited, and for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazinyl, 2-pyrimidyl. , 4-Pyrimidyl, 5-Pyrimidyl, 3-Pyridadyl, 4-Pyridadyl, 4- (1,2,3-Triazil), 5- (1,2,3-Triazil), 2- (1,3,5- Triazil), 3- (1,2,4-triazil), 5- (1,2,4-triazil), 6- (1,2,4-triazil), 2-quinoline, 3-quinolyl, 4-quinolyl , 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalyl, 3 -Kinoxalyl, 5-Kinoxalyl, 6-Kinoxalyl, 7-Kinoxalyl, 8-Kinoxalyl, 3-Synolyl, 4-Synolyl, 5-Synolyl, 6-Synnolyl, 7-Synolyl, 8-Synolyl, 2-Kinazolyl, 4-Kynazolyl , 5-Kinazolyl, 6-Kinazolyl, 7-Kinazolyl, 8-Kinazolyl, 1-phthalazyl, 4-phthalazyl, 5-phthalazyl, 6-phthalazyl, 7-phthalazyl, 8-phthalazyl, 1-tetrahydroquinoline, 2-tetrahydro Quinoline, 3-Tetrahydroquinoline, 4-Tetrahydroquinoline, 5-Tetrahydroquinoline, 6-Tetrahydroquinoline, 7-Tetrahydroquinoline, 8-Tetrahydroquinoline, 1-Pyrrolyl, 2-Pyrrolyl, 3-Pyrrolyl , 2-Frill, 3-Frill, 2-Thienyl, 3-Thienyl, 1-Imidazolyl, 2-Imidazolyl, 4-Imidazolyl, 5-Imidazolyl, 1-Pyrazolyl, 3-Pyrazolyl, 4-Pyrazolyl, 5-Pyrazolyl, 2 -Oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 4-( 1,2,3-thiadiazolyl), 5- (1,2,3-thiadiazolyl), 3- (1,2,5-thiadiazolyl), 2- (1,3,4-thiadiazolyl), 4- (1, 2,3-oxadiazolyl), 5- (1,2,3-oxadiazolyl), 3- (1,2,4-oxadiazolyl), 5- (1,2,4-oxadiazolyl), 3- (1,2,5-oxadiazolyl), 2- (1,3,4-oxadiazolyl), 1- (1,2,3-triazolyl), 4- (1,2,3-triazolyl), 5- (1,2,3-triazolyl), 1- (1,2,4-triazolyl), 3- (1,2,4-triazolyl), 5- (1,2,4-triazolyl), 1-tetrazolyl, 5-Tetrazolyl, 1-Indrill, 2-Indrill, 3-Indrill, 4-Indrill, 5-Indrill, 6-Indrill, 7-Indrill, 1-Isoindrill, 2-Isoindrill, 3-Isoindrill, 4-Isoindrill, 5- Isoindrill, 6-isoindrill, 7-isoindrill, 1-benzoimidazolyl, 2-benzoimidazolyl, 4-benzoimidazolyl, 5-benzoimidazolyl, 6-benzoimidazolyl, 7-benzoimidazolyl, 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, 7-benzofuranyl, 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofunyl, 2-benzo Thienyl, 3-benzothienyl, 4-benzothienyl, 5-benzothienyl, 6-benzothienyl, 7-benzothienyl, 2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6- Benzoxazolyl, 7-benzoxazolyl, 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl, 1-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6- Indazolyl, 7-Indazolyl, 2-morphoryl, 3-morphoryl, 4-morphoryl, 1-piperidyl, 2-piperazyl, 1-piperidyl, 2-piperidyl, 3-piperidyl, 4-piperidyl, 2-tetrahydropyranyl, 3- Tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothiopyranyl, 3-tetrahydrothiopyranyl, 4-tetrahydrothiopyranyl, 1-pyrrolidyl, 2-pyrrolidyl, 3-pyrrolidyl, furanyl, 2-tetrahydropyranyl, Examples thereof include 3-tetrahydropyran, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 5-methyl-3-oxo-2,3-dihydro-1H-pyrazole-4-yl group and the like.

The "alkyl group" in A in the above formula (2) is the same as the "alkyl group" in A in the above formula (1).

Among these, as A in the above formula (2), R ¹ and R ² are preferably hydrogen atoms, R ³ and R ⁴ are hydrogen atoms, or alkyl groups having 1 to 18 carbon atoms are preferable, and R ¹ and R ² are preferable. Is a hydrogen atom, R ³ and R ⁴ are more preferably alkyl groups having 1 to 12 carbon atoms, R ¹ and R ² are particularly preferably hydrogen atoms, and R ³ and R ⁴ are particularly preferably alkyl groups having 1 to 6 carbon atoms.

Among the compounds represented by the above formula (2), Z is an alkyl group having 6 to 35 carbon atoms, R ¹ and R ² of A are hydrogen atoms, and R ³ and R ⁴ are carbon atoms 1 to 18. Z is an alkyl group having 10 to 30 carbon atoms, R ¹ and R ² of A are hydrogen atoms, and R ³ and R ⁴ are alkyl groups having 1 to 12 carbon atoms. It is more preferable that Z is an alkyl group having 12 to 25 carbon atoms, R ¹ and R ² of A are hydrogen atoms, and R ³ and R ⁴ are alkyl groups having 1 to 6 carbon atoms. Especially preferable.

More specifically, the compound represented by the formula (2) is more preferably the compound represented by the following formula (2a).

〔式中、Ｚ´は炭素数６～２５のアルキル基であり、Ａ´は式（ia）又は（iia）であり、Ｒ^８、Ｒ^９、Ｒ^１０及びＲ^１１は、各々水素原子又は炭素数１～６のアルキル基を示す。〕

[In the formula, Z'is an alkyl group having 6 to 25 carbon atoms, A'is a formula (ia) or (iia), and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are hydrogen atoms or carbons, respectively. The number 1 to 6 alkyl groups are shown. ]

Among the compounds represented by the formula (2a), a compound in which Z'is an alkyl group having 6 to 25 carbon atoms is preferable, a compound having an alkyl group having 8 to 20 carbon atoms is more preferable, and a compound having 12 to 18 carbon atoms is more preferable. Compounds that are alkyl groups are more preferred.

In the case of the compound represented by the formula (2a) in which A'is the formula (ia), the compound in which R ⁸ and R ⁹ are hydrogen atoms is preferable.

In the case of a compound represented by the formula (2a) and in which A'is the formula (iia), a compound in which R ¹⁰ and R ¹¹ are alkyl groups each having 1 to 6 carbon atoms is preferable, and the compound has 1 carbon atom. Compounds of up to 5 alkyl groups are more preferred.

Among the compounds represented by the formula (2a), Z'is an alkyl group having 12 to 18 carbon atoms, A'is a group represented by the formula (ia), and R ⁸ and R ⁹ are hydrogen atoms. It is particularly preferable to have.

More specifically, the compounds represented by the formula (2) include heptane hydrazide, octane hydrazide, nonan hydrazide, decan hydrazide, dodecan hydrazide, pentadecane hydrazide, octadecane hydrazide, icosan hydrazide, pentacosan hydrazide, triacontan hydrazide, Examples thereof include tetraconta hydrazide, and among them, octadecane hydrazide is preferable.

In the rubber composition of the present invention, the compound represented by the formula (2) may contain only one kind selected from the above-mentioned compounds alone, or may contain two or more kinds in a mixture. good.

The compounding ratio of the compound represented by the formula (2) is preferably 0.01 to 30 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the rubber component of the component (a). Is more preferable. By blending in the ratio, the effect of improving processability can be effectively obtained.

The blending ratio of the component (b) and (c) is preferably component (b): component (c) = 1: 500 to 500: 1, and component (b): component (c) = 1: 100 to. It is more preferably 100: 1, and further preferably component (b): component (c) = 1: 20 to 20: 1.

Preferred combinations of the components (b) and (c) include, for example, as the component (b), pyridine-2-carbohydrazide, benzene-1,3-dicarbohydrazide, N'-(4-methylpentane-2). -Iriden) Pleid-2-Carbohydrazide At least one selected from the group and at least one selected from the group consisting of octadecanehydrazide, heptanehydrazide, octanehydrazide, dodecanehydrazide as component (c). Illustratively, specifically, component (b): pyridine-2-carbohydrazide and component (c): octadecane hydrazide, component (b): benzene-1,3-dicarbohydrazide and component (c): octadecane hydrazide. Or, component (b): N'-(4-methylpentane-2-iriden) pyridine-2-carbohydrazide and component (c): octadecanehydrazide are preferable, and component (b): pyridine-2- Carbohydrazide and component (c): octadecane hydrazide, or component (b): benzene-1,3-dicarbohydrazide and component (c): octadecane hydrazide are more preferred.

(1.4. Other ingredients)
In addition to the above-mentioned rubber components and compounds, the rubber composition of the present invention includes fillers and compounding agents commonly used in the rubber industry, such as antiaging agents, antioxidants, softeners, processing aids, and waxes. , Resin, foaming agent, oil, stearate, zinc oxide (ZnO), vulcanization accelerator, vulcanization retarder, vulcanization agent (sulfur), etc. are appropriately selected within a range that does not impair the object of the present invention. Can be blended.

As the filler, a known filler used in the rubber industry can be widely used. Specifically, carbon black and inorganic fillers can be exemplified, and of course, they are not limited thereto.

The carbon black is not particularly limited, and examples thereof include commercially available carbon black, carbon-silica dual phase filler, and the like.

Specifically, carbon black includes, for example, high, medium or low structure SAF, ISAF, IISAF, N110, N134, N220, N234, N330, N339, N375, N550, HAF, FEF, GPF, SRF grade carbon. Black and the like can be mentioned. Among them, preferable carbon blacks are SAF, ISAF, IISAF, N134, N234, N330, N339, N375, HAF, or FEF grade carbon black.

The amount of DBP absorbed by carbon black is not particularly limited, and is preferably 60 to 200 cm ^3/100 g, more preferably 70 to 180 cm ^3/100 g, and particularly preferably 80 to 160 cm ^3/100 g.

The nitrogen adsorption specific surface area of carbon black (measured according to N2SA, JIS K 6217-2: 2001) is preferably 30 to 200 m ² / g, more preferably 40 to 180 m ² / g, and particularly preferably 40 to 180 m 2 / g. It is 50 to 160 m ² / g.

The inorganic filler is not particularly limited as long as it is an inorganic compound usually used in the rubber industry. Examples of the inorganic compounds that can be used include alumina such as silica, γ-alumina and α-alumina (Al ₂ O ₃ ); alumina monohydrate such as boehmite and diaspore (Al ₂ O ₃・ H ₂ O); gibsite. , Aluminum hydroxide [Al (OH) ₃ ] such as Bayarite; Aluminum carbonate [Al ₂ (CO ₃ ) ₃ ], Magnesium hydroxide [Mg (OH) ₂ ], Magnesium oxide (MgO), Magnesium carbonate (MgCO ₃ ) ), Tarku (3MgO ・ 4SiO ₂・ H _2O ), Attapulsite (5MgO ・ 8SiO ₂・ 9H _2O ), Titanium White (TIO ₂ ), Titanium Black (TIO _2n-1 ), Calcium Oxide (CaO), Hydroxide Calcium [Ca ₍ OH) ₂ ], magnesium oxide ₍ MgO ・_Al2O3 ) _, clay _{( Al2O3.2SiO 2} ), kaolin _{( Al2O3.2SiO2.2H2O} ), pyrophyllite (Al ₂ O 3.4SiO ₂・ H ₂ O), _Bentnite (Al ₂ O _{3.4SiO 2.2H 2} O), Aluminum silicate ₍ Al ₂ SiO ₅ , Al _4.3SiO 4.5H ₂ O, etc.), Magnesium silicate (Mg ₂ SiO ₄ , MgSiO ₃ etc.), Calcium silicate (Ca ₂ · SiO ₄ etc.), Aluminum oxide calcium silicate (Al ₂ O ₃ · CaO · 2SiO ₂ etc.), Magnesium magnesium silicate (CaMgSiO ₄ etc.) ), Calcium carbonate (CaCO ₃ ), Zyla oxide (ZrO ₂ ), Zirconium hydroxide [ZrO (OH) ₂ · nH ₂ O], Zirconium carbonate [Zr (CO ₃ ) ₂ ], Charge correction like various zeolites Examples thereof include crystalline aluminosilicates containing hydrogen, alkali metals or alkaline earth metals. In these inorganic fillers, the surface of the inorganic filler may be organically treated in order to improve the affinity with the rubber component.

Among them, silica is preferable as the inorganic filler from the viewpoint of braking characteristics, and the BET specific surface area of silica is not particularly limited, and examples thereof include a range of 40 to 350 m ² / g. Silica having a BET specific surface area in this range has an advantage that it can achieve both rubber reinforcing properties and dispersibility in rubber components. The BET specific surface area is measured according to ISO 5794/1.

From this point of view, the preferred silica is silica having a BET specific surface area in the range of 50 to 350 m ² / g, more preferably silica having a BET specific surface area of 100 to 270 m ² / g, and particularly preferably. , BET specific surface area is silica in the range of 110 to 270 m ² / g.

Commercially available products of such silica include trade names "HD165MP" (BET specific surface area = 165m ² / g) and "HD115MP" (BET specific surface area = 115m ² / g) manufactured by Queuechen Silicon Chemical Co., Ltd. "HD200MP" (BET specific surface area = 200m ² / g), "HD250MP" (BET specific surface area = 250m ² / g), trade name "Nipseal AQ" manufactured by Toso Silica Co., Ltd. (BET specific surface area = 205m ² / g) ), "Nipseal KQ" (BET specific surface area = 240 m ² / g), trade name "Ultrazil VN3" manufactured by Degussa (BET specific surface area = 175 m ² / g), and the like.

The blending amount of the filler is preferably 20 to 120 parts by mass, more preferably 30 to 100 parts by mass, and further preferably 40 to 90 parts by mass with respect to 100 parts by mass of the rubber component. preferable.

Among the fillers, carbon black or silica is preferable. Each may be used alone or in combination.

It is particularly preferable that the rubber composition of the present invention contains silica, and silica may be added as the component (d) to the rubber composition of the present invention.

By containing silica, deterioration of processability can be further suppressed, and the effect of low heat generation inherent in the compound represented by the formula (1) can be sufficiently exhibited.

The blending amount of silica is preferably 5 to 120 parts by mass, more preferably 10 to 100 parts by mass, and further preferably 15 to 90 parts by mass with respect to 100 parts by mass of the rubber component. ..

Further, in the rubber composition containing the above-mentioned filler, a silane coupling agent and a titanate cup are used for the purpose of increasing the toughness of the rubber composition by the filler or increasing the tear strength and wear resistance of the rubber composition. A ring agent, an aluminate coupling agent, or a zirconate coupling agent may be blended.

The silane coupling agent that can be used in combination with the above-mentioned filler is not particularly limited, and a commercially available product can be preferably used. Examples of such a silane coupling agent include sulfide-based, polysulfide-based, thioester-based, thiol-based, olefin-based, epoxy-based, amino-based, and alkyl-based silane coupling agents.

Examples of the sulfide-based silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (3-methyldimethoxysilylpropyl) tetrasulfide, and bis ( 2-Triethoxysilylethyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxysilylpropyl) disulfide, bis (3-methyldimethoxysilylpropyl) disulfide, bis (2-triethoxysilylpropyl) disulfide Ethyl) disulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-trimethoxysilylpropyl) trisulfide, bis (3-methyldimethoxysilylpropyl) trisulfide, bis (2-triethoxysilylethyl) trisulfide Sulfide, bis (3-monoethoxydimethylsilylpropyl) tetrasulfide, bis (3-monoethoxydimethylsilylpropyl) trisulfide, bis (3-monoethoxydimethylsilylpropyl) disulfide, bis (3-monomethoxydimethylsilylpropyl) Tetrasulfide, bis (3-monomethoxydimethylsilylpropyl) trisulfide, bis (3-monomethoxydimethylsilylpropyl) disulfide, bis (2-monoethoxydimethylsilylethyl) tetrasulfide, bis (2-monoethoxydimethylsilylethyl) ) Trisulfide, bis (2-monoethoxydimethylsilylethyl) disulfide and the like. Of these, bis (3-triethoxysilylpropyl) tetrasulfide is particularly preferable.

Examples of the thioester-based silane coupling agent include 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, and 3-lauroylthiopropyltriethoxysilane. , 2-Hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxysilane, 3-hexanoylthiopropyltrimethoxysilane, 3-Octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-lauroylthiopropyltrimethoxysilane, 2-hexanoylthioethyltrimethoxysilane, 2-octanoylthioethyltrimethoxysilane, 2 -Decanoyylthioethyltrimethoxysilane, 2-lauroylthioethyltrimethoxysilane and the like can be mentioned.

Examples of the thiol-based silane coupling agent include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-[ethoxybis (3,6,9,12,15). -Pentaoxa-octacosane-1-yloxy) silyl] -1-propanethiol and the like can be mentioned.

Examples of the olefin-based silane coupling agent include dimethoxymethylvinylsilane, vinyltrimethoxysilane, dimethylethoxyvinylsilane, diethoxymethylvinylsilane, triethoxyvinylsilane, vinyltris (2-methoxyethoxy) silane, allyltrimethoxysilane, and allyltri. Ethoxysilane, p-styryltrimethoxysilane, 3- (methoxydimethoxydimethylsilyl) propyl acrylate, 3- (trimethoxysilyl) propyl acrylate, 3- [dimethoxy (methyl) silyl] propyl methacrylate, 3- (trimethoxysilyl) Examples thereof include propyl methacrylate, 3- [dimethoxy (methyl) silyl] propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, 3- [tris (trimethylsiloxy) silyl] propyl methacrylate and the like.

Examples of the epoxy-based silane coupling agent include 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane, diethoxy (3-glycidyloxypropyl) methylsilane, and triethoxy (3-glycidyloxypropyl) silane. , 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Of these, 3-glycidyloxypropyltrimethoxysilane is preferable.

Examples of the amino-based silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyl. Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-ethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl)- Examples thereof include 2-aminoethyl-3-aminopropyltrimethoxysilane. Of these, 3-aminopropyltriethoxysilane is preferable.

Examples of the alkyl-based silane coupling agent include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, and isobutyltriethoxy. Examples thereof include silane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane and the like. Of these, methyltriethoxysilane is preferred.

Among these silane coupling agents, bis (3-triethoxysilylpropyl) tetrasulfide can be particularly preferably used.

The titanate coupling agent that can be used in combination with the filler is not particularly limited, and a commercially available product can be preferably used. Examples of such titanate coupling agents include alkoxide-based, chelate-based, and acylate-based titanate coupling agents.

Examples of the alkoxide-based titanate coupling agent include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl titanate, tetratertiary butyl titanate, and tetrastearyl titanate. Of these, tetraisopropyl titanate is preferred.

Examples of the chelating titanate coupling agent include titanium acetylacetonate, titaniumtetraacetylacetonate, titaniumethylacetoacetate, titanium dodecylbenzenesulfonate compound, titanium phosphate compound, titaniumoctylene glycolate, and titaniumethylacetate acetate. , Titanium Lactate Ammium Salt, Titanium Lactate, Titanium Ethanol Aminate, Titanium Octylene Glycolate, Titanium Aminoethyl Amino Ethanolate and the like. Of these, titanium acetylacetonate is preferable.

Examples of the acylate-based titanate coupling agent include titanium isostearate and the like.

The aluminate coupling agent that can be used in combination with the filler is not particularly limited, and a commercially available product can be preferably used. Examples of such an aluminate coupling agent include 9-octadecenyl acetoacetate aluminum diisopropylate, aluminum secondary butoxide, aluminum tris acetylacetone, aluminum bisethyl acetoacetate monoacetyl acetone, and aluminum tris ethyl acetoacetate. Can be mentioned. Of these, 9-octadecenylacetate acetate aluminum diisopropylate is preferable.

The zirconate coupling agent that can be used in combination with the filler is not particularly limited, and a commercially available product can be preferably used. Examples of such a zirconate coupling agent include alkoxide-based, chelate-based, and acylate-based zirconate coupling agents.

Examples of the alkoxide-based zirconium-based coupling agent include normal propyl zirconate and normal butyl zirconate. Of these, normal butyl zirconate is preferable.

Examples of the chelate-based zirconate coupling agent include zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium ethylacetate acetate, and zirconium lactate ammonium salt. Of these, zirconium tetraacetylacetonate is preferable.

Examples of the acylate-based zirconate coupling agent include zirconium stearate and zirconium octylate. Of these, zirconium stearate is preferred.

In the present invention, the silane coupling agent, the titanate coupling agent, the aluminate coupling agent, and the zirconate coupling agent may be used alone or in combination of two or more.

The blending amount of the silane coupling agent is preferably 0.1 to 20 parts by mass, and more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the filler. When it is 0.1 part by mass or more, the effect of improving the tear strength of the rubber composition can be more preferably exhibited, and when it is 20 parts by mass or less, the cost of the rubber composition is reduced and the economic efficiency is improved. do.

(2. Tires)
By manufacturing a tire using the rubber composition of the present invention described above, a tire having excellent low heat generation can be obtained.

In the tire of the present invention, the rubber composition is used particularly for at least one member selected from a tread portion, a sidewall portion, a bead area portion, a belt portion, a carcass portion and a shoulder portion.

Among them, one of the most preferable embodiments is to form the tire tread portion of the pneumatic tire with the rubber composition.

The tread portion is a portion having a tread pattern and in direct contact with the road surface, and is a tire outer skin portion that protects the carcass portion and prevents wear and trauma, and is a cap tread and / or a cap tread that constitutes the ground contact portion of the tire. The base tread that is placed inside the tire.

The sidewall portion is, for example, a portion of a pneumatic radial tire from the lower side of the shoulder portion to the bead portion, which protects the carcass portion and is the portion most severely bent when traveling.

The bead area is a part that fixes both ends of the carcass cord and at the same time fixes the tire to the rim. A bead is a structure in which high carbon steel is bundled.

The belt portion is a reinforcing band stretched in the circumferential direction between the tread having a radial structure and the carcass. The carcass part is strongly tightened like a tub to increase the rigidity of the tread.

The carcass portion is a portion of the cord layer forming the skeleton of the tire, and plays a role of withstanding the load received by the tire, the impact, and the filling air pressure.

The shoulder part is the shoulder part of the tire and serves to protect the carcass part.

The tire of the present invention can be manufactured according to a method known so far in the field of tires. Further, as the gas to be filled in the tire, normal or air with adjusted oxygen partial pressure; an inert gas such as nitrogen, argon or helium can be used.

(3. Additives for rubber)
The rubber additive of the present invention contains the following components (b) and (c).
Component (b); compound represented by the following formula (1) Component (c); compound represented by the following formula (2)

〔式中、Ａは下記式（i）又は（ii）で示される基を示す。
式（i）又は（ii）において、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、各々水素原子又は炭素数１～１８のアルキル基を示す。
Ｘは、窒素含有複素環基、炭素数１～５のアルキル基、アリール基、又は基－Ｙ－ＣＯ－ＮＨＡを示す。或いは、Ｘは、基－ＣＨＲ^６－ＣＲ^５＝Ｎ－を介してＡと結合することにより環を形成してもよい。これら各基及び環は、さらに置換基を有していてもよい。
Ｙは、２価の窒素含有複素環基、炭素数１～１８のアルキレン基、又はアリーレン基を示す。
Ｒ^５は、水素原子、炭素数１～１８のアルキル基、又はアリール基を、

Ｒ^６は、水素原子、ハロゲン原子、アルキル基、アルケニル基、ヒドラジド基、アミノ基、チオカルボキシル基、又はチオール基を示し、これら各基は更に置換基を有していてもよい。
Ｚは、炭素数６～４０のアルキル基を示し、該アルキル基はさらに置換基を有していてもよい。〕

[In the formula, A represents a group represented by the following formula (i) or (ii).
In formula (i) or (ii), R ¹ , R ² , R ³ and R ⁴ represent hydrogen atoms or alkyl groups having 1 to 18 carbon atoms, respectively.
X represents a nitrogen-containing heterocyclic group, an alkyl group having 1 to 5 carbon atoms, an aryl group, or a group-Y-CO-NHA. Alternatively, X may form a ring by binding to A via the group -CHR ⁶ -CR ⁵ = N-. Each of these groups and rings may further have a substituent.
Y represents a divalent nitrogen-containing heterocyclic group, an alkylene group having 1 to 18 carbon atoms, or an arylene group.
R5 has a hydrogen atom, an alkyl group having ¹ to 18 carbon atoms, or an aryl group.

R ⁶ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydrazide group, an amino group, a thiocarboxyl group, or a thiol group, and each of these groups may further have a substituent.
Z represents an alkyl group having 6 to 40 carbon atoms, and the alkyl group may further have a substituent. ]

The components (b) and (c) contained in the rubber additive of the present invention are the same as the components (b) and (c) contained in the above-mentioned rubber composition of the present invention, and are used for the rubber. The rubber material obtained by using the additive has excellent low heat generation and processability, and can be suitably used for, for example, a tire.

The additive for rubber of the present invention can be used in a state where the compound represented by the formula (1), the compound represented by the formula (2) and the like are mixed. In that case, these compounds and the like may be weighed in a predetermined amount or an appropriate amount and mixed by a known method. Mixing can be performed by, for example, a rotary ball mill, a vibrating ball mill, a planetary mill, a paint shaker, a locking mill, a locking mixer, a bead mill, a stirrer, or the like, either wet or dry.

The blending ratio of the components (b) and (c) is preferably component (b): component (c) = 1: 500 to 500: 1, and component (b): component (c) = 100: 1 to 1. It is more preferably 1: 100, and further preferably component (b): component (c) = 1: 20 to 20: 1.

Preferred combinations of the components (b) and (c) include, for example, as the component (b), pyridine-2-carbohydrazide, benzene-1,3-dicarbohydrazide, N'-(4-methylpentane-2). -Iriden) Pleid-2-Carbohydrazide at least one selected from the group and at least one selected from the group consisting of octadecanehydrazide, heptanehydrazide, octanehydrazide, dodecanehydrazide as component (c). Illustratively, specifically, component (b): pyridine-2-carbohydrazide and component (c): octadecane hydrazide, component (b): benzene-1,3-dicarbohydrazide and component (c): octadecane hydrazide. Or, component (b): N'-(4-methylpentane-2-iriden) pyridine-2-carbohydrazide and component (c): octadecanehydrazide are preferable, and component (b): pyridine-2- Carbohydrazide and component (c): octadecane hydrazide, component (b): benzene-1,3-dicarbohydrazide and component (c): octadecane hydrazide are more preferable.

(4. Method for producing rubber composition)
The method for producing the rubber composition of the present invention is not particularly limited, and for example, the above-mentioned rubber component, the compound represented by the formula (1), the compound represented by the formula (2), and other if necessary. The ingredients can be obtained by mixing. Moreover, each of these compounds may be produced by a known method.

The above-mentioned method for mixing is not particularly limited, and a known method can be widely adopted. Specifically, the above-mentioned rubber component, the compound represented by the formula (1), the compound represented by the formula (2), and if necessary, other components are kneaded using a kneader or the like. The method can be mentioned.

Although the embodiments of the present invention have been described above, the present invention is not limited to these examples, and it is needless to say that the present invention can be implemented in various forms without departing from the gist of the present invention.

Hereinafter, embodiments of the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

Production Example 1: Production of 4H-1,2,4-triazole-3-carbohydrazide (Compound I-3) 12.5 g of methyl 4H-1,2,4-triazole-3-carboxylate was added to 100 mL of methanol. To the solution, 9.9 g of hydrazine monohydrate was added and refluxed for 15 hours. The reaction solution was cooled and the precipitated solid was filtered. The obtained solid was washed with methanol and dried to obtain 12.3 g (yield 98%) of the desired product.
^{1 1} H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 4.5 (br-s, 2H), 8.4 (br-s, 1H), 9.8 (br-s, 1H), 14. 5 (br-s, 1H)
Melting point: 208 ° C

Production Example 2: Production of pyrazine-2-carbohydrazide (Compound I-4) 6.5 g of hydrazine monohydrate was added to a solution of 70 mL of methanol containing 12.0 g of methyl pyrazine-2-carboxylate for 12 hours. It circulated. The reaction solution was cooled and the precipitated solid was filtered. The obtained solid was washed with methanol and dried to obtain 11.3 g (yield 94%) of the desired product.
^{1 1} H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 4.7 (br-s, 2H), 8.7 (m, 1H), 8.8 (d, 1H), 9.1 (d, 1H), 10.1 (br-s, 1H)
Melting point: 170 ° C

Production Example 3: Production of Isoquinoline-1-Carbohydrazide (Compound I-5) 27.8 g of concentrated sulfuric acid was added to a solution prepared by adding 10.4 g of isoquinoline-1-carboxylic acid to 150 mL of methanol, and the mixture was refluxed for 72 hours. The reaction solvent was distilled off under reduced pressure, the obtained residue solution was dissolved in 100 mL of dichloromethane, and a saturated aqueous solution of sodium carbonate was added under ice-cooling to adjust the pH to 8. Extract the organic layer twice with 50 mL of dichloromethane, add sodium sulfate, stir, filter, and distill off the organic solvent under reduced pressure to obtain 10.3 g of the desired methyl isoquinolin-1-carboxylate (yield 91%). Got
To 10.3 g of methyl isoquinoline-1-carboxylate obtained above, 50 mL of methanol and 15.4 g of hydrazine monohydrate were added, and the mixture was refluxed for 12 hours. The reaction mixture was cooled, the solvent was distilled off under reduced pressure, and then 200 mL of water was added to the residue to precipitate a solid. The precipitated solid was filtered, washed with methanol, and dried to obtain 8.3 g (yield 81%) of the desired product.
^{1 1} H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 4.7 (br-s, 2H), 7.7 (m, 1H), 7.8 (m, 1H), 7.98 (d, 1H), 8.04 (d, 1H), 8.5 (d, 1H), 8.7 (dd, 1H), 9.9 (br-s, 1H)
Melting point: 107 ° C

Production Example 4: To a solution prepared by adding 25 g of 2-cyanopyrimidine to 50 mL of production water of pyrimidine-2-carbohydrazide (Compound I-6), 80 g of 25% caustic water was added, and the mixture was stirred at 60 ° C. for 2 hours. After stirring, the mixture was ice-cooled, the pH was adjusted to 3.8 using concentrated hydrochloric acid, and the mixture was stirred at room temperature for 1 hour. Next, the solvent was distilled off under reduced pressure, 50 mL of toluene was added, and the mixture was azeotropically heated. To the obtained crystals, 100 mL of methanol and 20 g of concentrated sulfuric acid were added, and the mixture was refluxed for 12 hours. The solvent was distilled off under reduced pressure, a saturated aqueous sodium hydrogen carbonate solution was added to the residue to adjust the pH to 7, and water was added to dissolve the salt. The organic layer was extracted three times with 50 mL of dichloromethane, sodium sulfate was added, the mixture was stirred, filtered, and the organic solvent was distilled off under reduced pressure to obtain 12.6 g (yield 38%) of methyl pyrimidine-2-carboxylate. rice field.
To 8.3 g of methylpyrimidine-2-carboxylate obtained above, 100 mL of methanol and 4.5 g of hydrazine monohydrate were added, and the mixture was refluxed for 12 hours. The reaction solution was cooled and the precipitated solid was filtered. The obtained solid was washed with methanol and dried to obtain 7.6 g (yield 92%) of the desired product.
^{1 1} H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 4.6 (br-s, 2H), 7.6 (t, 1H), 8.9 (d, 2H), 10.0 (br- s, 1H)
Melting point: 180 ° C

Production Example 5: Production of pyridazine-3-carbohydrazide (Compound I-7) 27.2 g of thionyl chloride is added to a solution prepared by adding 5.5 g of pyridazine-4-carboxylic acid to 50 mL of chloroform, and 6 at an outside temperature of 65 ° C. Stir for hours. After gradually adding 50 mL of methanol under ice-cooling, the solvent was distilled off under reduced pressure. 50 mL of dichloromethane was added to the residue, and an aqueous sodium hydrogen carbonate solution was added while stirring under ice-cooling to adjust the pH to 7.8. The precipitated solid is filtered, the solution is extracted three times with 100 mL of dichloromethane, sodium sulfate is added, the mixture is stirred, filtered, and the organic solvent is distilled off under reduced pressure to obtain 5.8 g of methyl pyridazine-4-carboxylate (collected). Rate 94%) was obtained.
To 4.8 g of methyl pyridazine-4-carboxylate obtained above, 50 mL of methanol and 4.5 g of hydrazine monohydrate were added and refluxed for 12 hours. The reaction solution was cooled and the solvent was distilled off under reduced pressure to obtain an oily product. Toluene 20 mL was added to the obtained product and azeotropically heated. By drying the solid obtained by azeotrope, 4.7 g (yield 98%) of the target product was obtained.
^{1 1} H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 4.7 (br-s, 2H), 7.9 (m, 1H), 8.1 (dd, 1H), 9.4 (dd, dd, 1H), 10.4 (br-s, 1H)
Melting point: 143 ° C

Production Example 6: Production of pyridazine-4-carbohydrazide (Compound I-8) 50 g of selenium dioxide is added to a solution prepared by adding 25.5 g of 3-methylpyridazine to 1.2 L of pyridine, and the mixture is stirred at an outside temperature of 80 ° C. for 12 hours. did. The reaction mixture was cooled to room temperature, the solid was removed with a hydrophilic PTFE membrane filter, and the solvent was distilled off under reduced pressure. 500 mL of methanol and 90 g of concentrated sulfuric acid were added to the residue, and the mixture was refluxed at an outside temperature of 80 ° C. for 12 hours. The solvent was distilled off under reduced pressure, and the pH of the residue was adjusted to 7.7 with a saturated aqueous sodium hydrogen carbonate solution. The solution was extracted four times with 100 mL of dichloromethane, sodium sulfate was added, the mixture was stirred, filtered, and the organic solvent was distilled off under reduced pressure to obtain 23.6 g (yield 63%) of methylpyridazine-3-carboxylate. ..
To 11.6 g of methyl pyridazine-3-carboxylate obtained above, 100 mL of methanol and 8.3 g of hydrazine monohydrate were added and refluxed for 1 hour. The reaction was cooled and the solvent was evaporated under reduced pressure to give a solid product. This product was crushed and washed with methanol, filtered, and dried to obtain 6.0 g (yield 52%) of the desired product.
^{1 1} H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 4.7 (br-s, 2H), 8.0 (dd, 1H), 9.4 (dd, 1H), 9.5 (m, 1H), 10.3 (br-s, 1H)
Melting point: 119 ° C

Production Example 7: Production of 2- (1H-benz [d] imidazol-1-yl) acetohydrazide (Compound I-9) A solution of 200 mL of dimethylformamide plus 6.1 g of sodium hydride was cooled to 0 ° C. 15.0 g of benzimidazole was added in divided portions. After stirring at room temperature for 1 hour, the mixture was cooled to 0 ° C., and 23.3 g of methyl bromoacetate was added dropwise. The reaction mixture was stirred at room temperature for 17 hours, neutralized with an aqueous ammonium chloride solution, separated with ethyl acetate, the solvent was distilled off, and then 200 mL of methanol and 25 g of hydrazine monohydrate were added. The reaction mixture was stirred at 50 ° C. for 18 hours, the solvent was distilled off, and the precipitated solid was recrystallized from 2-propanol to obtain 6.4 g (yield 26%) of the desired product.
^{1 1} H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 4.3 (brs, 2H), 7.2 (m, 2H), 7.5 (m, 1H), 7.7 (m, 1H) , 8.2 (s, 1H), 9.5 (brs, 1H), NH2 × 2 (4H) Undetected melting point: 252 ° C.

Production Example 8: Production of 2-amino-4- (methylsulfanyl) butanehydrazide (Compound I-10) A solution prepared by adding 5.0 g of methionine methyl hydrochloride to 25.0 mL of methanol was cooled to 0 ° C. and hydrazine was added to water. 3.13 g of Japanese product was added. The reaction mixture was stirred at 65 ° C. for 18 hours, cooled to room temperature, 1.35 g of sodium methoxide was added, and the mixture was stirred for 3 hours. After distilling off the solvent, the precipitated solid was filtered and dried to obtain 2.5 g (yield 60%) of the liquid target product.
^{1 1} H-NMR (400 MHz, CDCl ₃ , δ ppm): 1.58 (m, 1H), 1.75 (m, 1H), 1.59 (m, 2H), 2.03 (m, 3H), 2 .50 (m, 2H), 3.20 (m, 1H), 8.99 (br-s, 1H), NH2 × 2 (4H) undetected

Production Example 9: Production of 2-amino-3- (dodecylsulfanyl) propanehydrazide (Compound I-11) AIBN 2.51 g in a solution prepared by adding 5.57 g of L-cysteine ethyl hydrochloride and 16.0 g of dodecene to 110 mL of dichloromethane. Was added, and the mixture was stirred at 40 ° C. for 24 hours. After distilling off the solvent, 60 mL of methanol and 3.75 g of hydrazine monohydrate were added. The reaction mixture was stirred at 65 ° C. for 18 hours, and the precipitated solid was filtered and dried to obtain 5.96 g (yield 65%) of the desired product.
^{1 1} H-NMR (400 MHz, CDCl ₃ , δ ppm): 0.88 (t, 3H), 1.36 (m, 18H), 1.60 (m, 2H), 2.51 (m, 2H), 2 .70 (m, 1H), 3.01 (m, 1H), 3.55 (m, 1H), 8.37 (br-s, 1H)
Melting point: 57 ° C

Production Example 10: Production of N'-(4-Methylpentane-2-iriden) Pyridine-2-Carbohydrazide (Compound I-12) 14.6 g of methyl isobutyl ketone in a solution prepared by adding 10 g of picolinic acid hydrazide to 20 ml of methanol. Was added and refluxed overnight. The solvent was distilled off under reduced pressure to obtain an oily crude product. When 20 ml of isopropanol was added and stirred under ice-cooling, crystals were precipitated. 30 ml of isopropanol was used as a washing solution and filtered, and the obtained white solid was dried under reduced pressure to obtain 15.6 g (yield 98%) of the desired product.
^{1 1} H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 0.91-0.96 (m, 6H), 1.97-2.04 (m, 4H), 2.21-2.29 (m) , 2H), 7.64-7.67 (m, 1H), 8.03-8.11 (m, 2H), 8.68-8.69 (m, 1H), 10.75-10.85 (M, 1H)
Melting point: 84 ° C

Production Example 11: Production of N'-(Propane-2-iriden) Pyridine-2-Carbohydrazide (Compound I-13) To 3.0 g of picolinic acid hydrazide, 25 mL of acetone was added and refluxed for 21 hours. The reaction solution was cooled and the precipitated solid was filtered. The obtained solid was washed with methanol and dried to obtain 3.7 g (yield 95%) of the desired product.
^{1 1} H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 1.98 (s, 3H), 2.04 (s, 3H), 7.65 (m, 1H), 8.06 (m, 2H) , 8.68 (m, 1H), 10.8 (s, 1H)
Melting point: 100 ° C

Production Example 12: Production of N'-(Tridecane-2-iriden) Pyridine-2-Carbohydrazide (Compound I-14) 14.5 g of 2-tridecaneone was added to a solution of 30 mL of methanol containing 5.0 g of hydrazide picolinate. In addition, reflux was performed for 18 hours. The reaction mixture was cooled, and the residue was purified by silica gel column chromatography to obtain 10.6 g (yield 92%) of the desired product.
^{1 1} H-NMR (400 MHz, CDCl ₃ , δ ppm): 0.88 (t, 3H), 1.31 (m, 16H), 1.59 (m, 2H), 2.03 (s, 3H), 2 .44 (m, 2H), 7.46 (m, 1H), 7.87 (m, 1H), 8.30 (m, 1H), 8.55 (m, 1H), 10.68 (br- s, 1H)
Melting point: 44 ° C

Production Example 13: Production of pyridine-3,5-dicarbohydrazide (Compound II-2) 8.66 g of hydrazine monohydrate was added to a solution of 70 mL of methanol containing 15.9 g of diethyl 3,5-pyridinedicarboxylic acid. It was added and refluxed for 24 hours. The reaction solution was cooled and the precipitated solid was filtered. The obtained solid was washed with methanol and dried to obtain 13.9 g (yield: 99%) of the desired product.
^{1 1} H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 4.6 (br-s, 4H), 8.5 (t, 1H), 9.0 (d, 2H), 10.0 (br- s, 2H)
Melting point: 234 ° C

Production Example 14: Production of heptane hydrazide (Compound IV-2) 3.05 g of hydrazine monohydrate was added to a solution prepared by adding 5.77 g of methyl heptate to 40 mL of methanol, and the mixture was refluxed for 18 hours. After distilling off the solvent, the precipitated solid was filtered. The obtained solid was washed with methanol and dried to obtain 4.61 g (yield: 80%) of the desired product.
^{1 1} H-NMR (400 MHz, CDCl ₃ , δ ppm): 0.88 (t, 3H), 1.32 (m, 6H), 1.66 (m, 2H), 2.15 (m, 2H), 3 .90 (br-s, 2H), 6.75 (br-s, 1H)
Melting point: 83 ° C

Production Example 15: Production of N'-(Propane-2-iriden) octadecane hydrazide (Compound IV-4) To a solution prepared by adding 2.3 g of stearic acid hydrazide to 25 mL of ethanol, 25 mL of acetone was added and refluxed for 12 hours. The reaction solution was cooled and the precipitated solid was filtered. The obtained solid was washed with ethanol and dried to obtain 2.6 g (yield 99%) of the desired product.
^{1 1} H-NMR (400 MHz, CDCl ₃ , δ ppm): 0.8 (t, 3H), 1.3 (m, 28H), 1.7 (m, 2H), 1.8 (s, 3H), 2 .0 (s, 3H), 2.6 (t, 2H), 8.1 (s, 1H)
Melting point: 75 ° C

Production Example 16: Production of N'-(4-methylpentane-2-iriden) octadecane hydrazide (Compound IV-5) Add 4.2 g of methyl isobutyl ketone to a solution of 25 mL of butanol plus 4.2 g of hydrazide stearate. It was refluxed for 21 hours. The reaction solution was cooled and the precipitated solid was filtered. The obtained solid was washed with methanol and dried to obtain 5.1 g (yield 95%) of the desired product.
^{1 1} H-NMR (400 MHz, CDCl ₃ , δ ppm): 0.88 (t, 3H), 0.92 (d, 6H), 1.3 (m, 28H), 1.7 (m, 2H), 1 .8 (s, 3H), 2.0 (m, 1H), 2.1 (d, 2H), 2.6 (t, 2H), 8.1 (s, 1H), NH2 (2H) undetected Melting point: 74 ° C

Production Example 17: Production of hexanehydrazide (Compound A) 3.00 g of hydrazine monohydrate was added to a solution prepared by adding 5.21 g of methyl caproate to 40 mL of methanol, and the mixture was refluxed for 18 hours. After distilling off the solvent, the precipitated solid was filtered. The obtained solid was washed with methanol and dried to obtain 4.01 g (yield: 77%) of the desired product.
^{1 1} H-NMR (400 MHz, CDCl ₃ , δ ppm): 0.88 (t, 3H), 1.33 (m, 4H), 1.66 (m, 2H), 2.15 (m, 2H), 3 .90 (br-s, 2H), 6.79 (br-s, 1H)
Melting point: 75 ° C

Examples 1 to 17, Comparative Examples 1 to 22, and Reference Examples 1 to 2: Production of rubber composition Each component shown in step A of Tables 1 and 2 below is mixed at the ratio (part by mass), and a Banbury mixer is used. Mixed in. After curing until the temperature of the mixture becomes 60 ° C or lower, each component shown in steps B of Tables 1 and 2 is added at the ratio (part by mass), and the maximum temperature of the mixture is adjusted to 70 ° C or lower. While mixing, a rubber composition was produced.

Low heat generation (Tan δ value index) test For the rubber compositions of each example and comparative example, the Tan δ value was measured at a temperature of 40 ° C., a dynamic strain of 5%, and a frequency of 15 Hz using a viscoelasticity measuring device (manufactured by Metarivib). did. For comparison, rubber compositions (Reference Examples 1 and 2) were prepared by the same formulation and the same manufacturing method as in each example except that no compound was added, and the rubber compositions (Reference Examples 1 and 2) were expressed by an index with the Tan δ value as 100, and the following formula was used. The hypocalidity index was calculated based on. The smaller the value of the low heat generation index, the lower the heat generation and the smaller the hysteresis loss.
Formula: Low exothermic index = (Tanδ value of rubber compositions of Examples 1 to 2 and 4 to 17, and Comparative Examples 1 to 2 and 4 to 22) × 100 / (Tanδ value of Reference Example 1)

Formula: Low exothermic index = (Tanδ value of rubber composition of Example 3 and Comparative Example 3) × 100 / (Tanδ value of Reference Example 2)

Workability ( Mooney Viscosity Index) Test Measured according to JIS K6300-1 (How to determine viscosity and scorch time with Mooney viscometer; ML1 + 4,100 ° C.). For comparison, rubber compositions (Reference Examples 1 and 2) were prepared using the same formulation and the same manufacturing method as in each example except that no compound was added, and the rubber compositions (Reference Examples 1 and 2) were represented by an index with the Mooney viscosity value as 100. The workability index was calculated based on the formula. The smaller the value of the workability index, the better the workability.
Formula: Workability index = (Moony viscosity value of rubber compositions of Examples 1 to 2 and 4 to 17 and Comparative Examples 1 to 2 and 4 to 22) × 100 / (Mooney viscosity value of Reference Example 1) )

Formula: Workability index = (Mooney viscosity value of rubber composition of Example 3 and Comparative Example 3) × 100 / (Mooney viscosity value of Reference Example 2)

※１：天然ゴム；ＧＵＡＮＧＫＥＮ ＲＵＢＢＥＲ社製、ＴＳＲ－２０
※２：化合物Ｉ－１；東京化成工業社製、ピリジン－３－カルボヒドラジド
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※２１：シリカ；ＱｕｅＣｈｅｎ Ｓｉｌｉｃｏｎ Ｃｈｅｍｉｃａｌ Ｃｏ．，Ｌｔｄ．社製、ＨＤ１６５ＭＰ
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※３０：硫黄；Ｓｈａｎｇｈａｉ Ｊｉｎｇｈａｉ Ｃｈｅｍｉｃａｌ Ｃｏ．，Ｌｔｄ社製

* 1: Natural rubber; TSR-20 manufactured by GUANGKEN RUBBER
* 2: Compound I-1; Pyridine-3-carbohydrazide manufactured by Tokyo Chemical Industry Co., Ltd. * 3: Compound I-2; Pyridine-2-carbohydrazide manufactured by Tokyo Chemical Industry Co., Ltd.
* 4: Compound I-3; 4H-1,2,4-triazole-3-carbohydrazide produced in Production Example 1
* 5: Compound I-4; Pyridazine-2-carbohydrazide produced in Production Example 2 * 6: Compound I-5; Isoquinolin-1-carbohydrazide produced in Production Example 3 * 7: Compound I-6; Production Example Pyrimidine-2-carbohydrazide produced in 4: Compound I-7; Pyridazine-3-carbohydrazide produced in Production Example 5 * 9: Pyridazine-4-carbohydrazide produced in Production Example 6 * 10: Compound I-9; 2- (1H-benzo [d] imidazole-1-yl) acetohydrazide produced in Production Example 7
* 11: Compound I-10; 2-amino-4- (methylsulfanyl) butane hydrazide produced in Production Example 8 * 12: Compound I-11; 2-amino-3- (dodecylsulfanyl) produced in Production Example 9 Propane hydrazide
* 13: Compound I-12; N'-(4-methylpentane-2-iriden) pyridine-2-carbohydrazide produced in Production Example 10
* 14: Compound I-13; N'-(propane-2-iriden) pyridine-2-carbohydrazide produced in Production Example 11
* 15: Compound I-14; N'-(tridecane-2-iriden) pyridine-2-carbohydrazide produced in Production Example 12
* 16: Compound IV-1; Octadecane hydrazide manufactured by Tokyo Chemical Industry Co., Ltd.
* 17: Compound IV-2; Heptane hydrazide produced in Production Example 14
* 18: Compound IV-3; Octane Hydrazide manufactured by Tokyo Chemical Industry Co., Ltd.
* 19: Compound A; Hexane hydrazide produced in Production Example 17.
* 20: Sodium stearate; manufactured by Tokyo Chemical Industry Co., Ltd. * 21: Silica; QueChen Silicon Chemical Co., Ltd. , Ltd. Made by HD165MP
* 22: Carbon black; Cabot, N234
* 23: Silane coupling agent; manufactured by Evonik, Si69
* 24: Anti-aging agent (N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine); Kemai Chemical Co., Ltd. , Ltd. * 25: Wax; Rhein Chemie Rheinau, Inc., Antilux 111
* 26: Zinc oxide; Darian Zinc Oxide Co., Ltd. , Ltd. * 27: Stearic acid; Sichuan Tianyu Grace Co., Ltd. * 28: Vulcanization accelerator A; Kemai Chemical Co., Ltd. , Ltd., CBS
* 29: Vulcanization accelerator B; Chemai Chemical Co., Ltd. , Ltd., DPG
* 30: Sulfur; Shanghai Jinghai Chemical Co., Ltd. , Made by Ltd

※１：天然ゴム；ＧＵＡＮＧＫＥＮ ＲＵＢＢＥＲ社製、ＴＳＲ－２０
※２：化合物Ｉ－１；東京化成工業社製、ピリジン－３－カルボヒドラジド
※３：化合物Ｉ－２；東京化成工業社製、ピリジン－２－カルボヒドラジド
※４：化合物Ｉ－３；製造例１で製造した４Ｈ－１，２，４－トリアゾール－３－カルボヒドラジド
※５：化合物Ｉ－４；製造例２で製造したピラジン－２－カルボヒドラジド
※６：化合物Ｉ－５；製造例３で製造したイソキノリン－１－カルボヒドラジド
※７：化合物Ｉ－６；製造例４で製造したピリミジン－２－カルボヒドラジド
※８：化合物Ｉ－７；製造例５で製造したピリダジン－３－カルボヒドラジド
※９：化合物Ｉ－８；製造例６で製造したピリダジン－４－カルボヒドラジド
※１０：化合物Ｉ－９；製造例７で製造した２－（１Ｈ－ベンゾ［ｄ］イミダゾール－１－イル）アセトヒドラジド
※１１：化合物Ｉ－１０；製造例８で製造した２－アミノ－４－（メチルスルファニル）ブタンヒドラジド
※１２：化合物Ｉ－１１；製造例９で製造した２－アミノ－３－（ドデシルスルファニル）プロパンヒドラジド
※１３：化合物Ｉ－１２；製造例１０で製造したＮ’－（４－メチルペンタン－２－イリデン）ピリジン－２－カルボヒドラジド
※１４：化合物Ｉ－１３；製造例１１で製造したＮ’－（プロパン－２－イリデン）ピリジン－２－カルボヒドラジド
※１５：化合物Ｉ－１４；製造例１２で製造したＮ’－（トリデカン－２－イリデン）ピリジン－２－カルボヒドラジド
※１６：化合物ＩＶ－１；東京化成工業社製、オクタデカンヒドラジド
※１７：化合物ＩＶ－２；製造例１４で製造したヘプタンヒドラジド
※１８：化合物ＩＶ－３；東京化成工業社製、オクタンヒドラジド
※１９：化合物Ａ；製造例１７で製造したヘキサンヒドラジド
※２０：ステアリン酸ナトリウム；東京化成工業社製
※２１：シリカ；ＱｕｅＣｈｅｎ Ｓｉｌｉｃｏｎ Ｃｈｅｍｉｃａｌ Ｃｏ．，Ｌｔｄ．社製、ＨＤ１６５ＭＰ
※２２：カーボンブラック；Ｃａｂｏｔ社製、Ｎ２３４
※２３：シランカップリング剤；エボニック社製、Ｓｉ６９
※２４：老化防止剤（Ｎ－フェニル－Ｎ'－（１,３－ジメチルブチル）－ｐ－フェニレンジアミン）；Ｋｅｍａｉ Ｃｈｅｍｉｃａｌ Ｃｏ．，Ｌｔｄ社製
※２５：ワックス；Ｒｈｅｉｎ Ｃｈｅｍｉｅ Ｒｈｅｉｎａｕ社製、Ａｎｔｉｌｕｘ １１１
※２６：酸化亜鉛；Ｄａｌｉａｎ Ｚｉｎｃ Ｏｘｉｄｅ Ｃｏ．，Ｌｔｄ社製
※２７：ステアリン酸；Ｓｉｃｈｕａｎ Ｔｉａｎｙｕ Ｇｒｅａｓｅ社製
※２８：加硫促進剤Ａ；Ｋｅｍａｉ Ｃｈｅｍｉｃａｌ Ｃｏ．，Ｌｔｄ社製、ＣＢＳ
※２９：加硫促進剤Ｂ；Ｋｅｍａｉ Ｃｈｅｍｉｃａｌ Ｃｏ．，Ｌｔｄ社製、ＤＰＧ
※３０：硫黄；Ｓｈａｎｇｈａｉ Ｊｉｎｇｈａｉ Ｃｈｅｍｉｃａｌ Ｃｏ．，Ｌｔｄ社製

* 1: Natural rubber; TSR-20 manufactured by GUANGKEN RUBBER
* 2: Compound I-1; Pyridine-3-carbohydrazide manufactured by Tokyo Chemical Industry Co., Ltd. * 3: Compound I-2; Pyridine-2-carbohydrazide manufactured by Tokyo Chemical Industry Co., Ltd.
* 4: Compound I-3; 4H-1,2,4-triazole-3-carbohydrazide produced in Production Example 1
* 5: Compound I-4; Pyridazine-2-carbohydrazide produced in Production Example 2 * 6: Compound I-5; Isoquinolin-1-carbohydrazide produced in Production Example 3 * 7: Compound I-6; Production Example Pyrimidine-2-carbohydrazide produced in 4: Compound I-7; Pyridazine-3-carbohydrazide produced in Production Example 5 * 9: Pyridazine-4-carbohydrazide produced in Production Example 6 * 10: Compound I-9; 2- (1H-benzo [d] imidazole-1-yl) acetohydrazide produced in Production Example 7
* 11: Compound I-10; 2-amino-4- (methylsulfanyl) butane hydrazide produced in Production Example 8 * 12: Compound I-11; 2-amino-3- (dodecylsulfanyl) produced in Production Example 9 Propane hydrazide
* 13: Compound I-12; N'-(4-methylpentane-2-iriden) pyridine-2-carbohydrazide produced in Production Example 10
* 14: Compound I-13; N'-(propane-2-iriden) pyridine-2-carbohydrazide produced in Production Example 11
* 15: Compound I-14; N'-(tridecane-2-iriden) pyridine-2-carbohydrazide produced in Production Example 12
* 16: Compound IV-1; Octadecane hydrazide manufactured by Tokyo Chemical Industry Co., Ltd.
* 17: Compound IV-2; Heptane hydrazide produced in Production Example 14
* 18: Compound IV-3; Octane Hydrazide manufactured by Tokyo Chemical Industry Co., Ltd.
* 19: Compound A; Hexane hydrazide produced in Production Example 17.
* 20: Sodium stearate; manufactured by Tokyo Chemical Industry Co., Ltd. * 21: Silica; QueChen Silicon Chemical Co., Ltd. , Ltd. Made by HD165MP
* 22: Carbon black; Cabot, N234
* 23: Silane coupling agent; manufactured by Evonik, Si69
* 24: Anti-aging agent (N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine); Kemai Chemical Co., Ltd. , Ltd. * 25: Wax; Rhein Chemie Rheinau, Inc., Antilux 111
* 26: Zinc oxide; Darian Zinc Oxide Co., Ltd. , Ltd. * 27: Stearic acid; Sichuan Tianyu Grace Co., Ltd. * 28: Vulcanization accelerator A; Kemai Chemical Co., Ltd. , Ltd., CBS
* 29: Vulcanization accelerator B; Chemai Chemical Co., Ltd. , Ltd., DPG
* 30: Sulfur; Shanghai Jinghai Chemical Co., Ltd. , Made by Ltd

Examples 18 to 22, Comparative Examples 16, 23 to 27, and Reference Examples 1 to 3: Production of rubber composition Each component shown in step A of Table 3 below is mixed at the ratio (part by mass), and a Banbury mixer is used. Mixed in. After curing until the temperature of the mixture becomes 60 ° C or lower, each component shown in step B in Table 3 is added at the ratio (part by mass), and the maximum temperature of the mixture is adjusted to 70 ° C or lower. Mixing was made to produce a rubber composition.

Low heat generation (Tan δ value index) test For the rubber compositions of each example and comparative example, the Tan δ value was measured at a temperature of 40 ° C., a dynamic strain of 5%, and a frequency of 15 Hz using a viscoelasticity measuring device (manufactured by Metarivib). did. For comparison, rubber compositions (Reference Examples 1 to 3) were prepared with the same formulation contents and the same manufacturing method as in each example except that no compound was added, and the rubber compositions (Reference Examples 1 to 3) were prepared and expressed by an index with the Tan δ value as 100, using the following formula. The hypocalidity index was calculated based on. The smaller the value of the low heat generation index, the lower the heat generation and the smaller the hysteresis loss.
Formula: Low exothermic index = (Tanδ value of rubber compositions of Examples 18 and 21-22, and Comparative Examples 16 and 26-27) × 100 / (Tanδ value of Reference Example 1)

Formula: Low exothermic index = (Tanδ value of rubber composition of Example 19 and Comparative Example 24) × 100 / (Tanδ value of Reference Example 2)

Formula: Low exothermic index = (Tanδ value of rubber composition of Example 20 and Comparative Example 25) × 100 / (Tanδ value of Reference Example 3)

Workability ( Mooney Viscosity Index) Test Measured according to JIS K6300-1 (How to determine viscosity and scorch time with Mooney viscometer; ML1 + 4,100 ° C.). For comparison, rubber compositions (Reference Examples 1 to 3) were prepared with the same formulation contents and the same manufacturing method as in each example except that no compound was added, and the rubber compositions (Reference Examples 1 to 3) were prepared and expressed by an index with the Mooney viscosity value as 100. The workability index was calculated based on the formula. The smaller the value of the workability index, the better the workability.
Formula: Workability index = (Moony viscosity value of rubber compositions of Examples 18 and 21 to 22, and Comparative Examples 16 and 26 to 27) × 100 / (Mooney viscosity value of Reference Example 1)

Formula: Workability index = (Mooney viscosity value of rubber composition of Example 19 and Comparative Example 24) × 100 / (Mooney viscosity value of Reference Example 2)

Formula: Workability index = (Mooney viscosity value of rubber composition of Example 20 and Comparative Example 25) × 100 / (Mooney viscosity value of Reference Example 3)

※３１：化合物ＩＩ－１；ベンゼン－１，３－ジカルボヒドラジド、大塚化学社製
※３２：化合物ＩＩ－２；製造例１３で製造したピリジン－３，５－ジカルボヒドラジド
※３３：化合物ＩＩＩ－１；３－メチル－５－ピラゾロン、大塚化学社製

* 31: Compound II-1; Benzene-1,3-dicarbohydrazide, manufactured by Otsuka Chemical Co., Ltd. * 32: Compound II-2; Pyridine-3,5-dicarbohydrazide produced in Production Example 13 * 33: Compound III -1; 3-Methyl-5-pyrazolone, manufactured by Otsuka Chemical Co., Ltd.

Examples 23 to 24, Comparative Examples 2, 28 to 29, and Reference Example 1: Production of a rubber composition Each component shown in step A of Table 4 below is mixed in its proportion (part by mass) and mixed with a Banbury mixer. did. After curing until the temperature of the mixture becomes 60 ° C or lower, each component shown in step B in Table 4 is added at the ratio (part by mass), and the maximum temperature of the mixture is adjusted to 70 ° C or lower. Mixing was made to produce a rubber composition.

Low heat generation (Tan δ value index) test For the rubber compositions of each example and comparative example, the Tan δ value was measured at a temperature of 40 ° C., a dynamic strain of 5%, and a frequency of 15 Hz using a viscoelasticity measuring device (manufactured by Metarivib). did. For comparison, a rubber composition (Reference Example 1) was prepared by the same formulation and the same manufacturing method as in each example except that no compound was added, and the rubber composition was expressed by an index with the Tan δ value as 100, based on the following formula. The low exothermic index was calculated. The smaller the value of the low heat generation index, the lower the heat generation and the smaller the hysteresis loss.
Formula: Low exothermic index = (Tanδ value of rubber compositions of Examples 23 to 24 and Comparative Examples 2 and 28 to 29) × 100 / (Tanδ value of Reference Example 1)

Workability ( Mooney Viscosity Index) Test Measured according to JIS K6300-1 (How to determine viscosity and scorch time with Mooney viscometer; ML1 + 4,100 ° C.). For comparison, a rubber composition (Reference Example 1) was prepared with the same compounding content and the same manufacturing method as in each example except that no compound was added, and the rubber composition was expressed by an index with the Mooney viscosity value as 100, using the following formula. The workability index was calculated based on this. The smaller the value of the workability index, the better the workability.
Formula: Workability index = (Moony viscosity value of rubber compositions of Examples 23 to 24 and Comparative Examples 2 and 28 to 29) × 100 / (Mooney viscosity value of Reference Example 1)

※３４：化合物ＩＶ－４；製造例１５で製造されたＮ’－（プロパン－２－イリデン）オクタデカンヒドラジド
※３５：化合物ＩＶ－５；製造例１６で製造されたＮ’－（４－メチルペンタン－２－イリデン）オクタデカンヒドラジド

* 34: Compound IV-4; N'-(propane-2-iriden) octadecane hydrazide produced in Production Example 15.
* 35: Compound IV-5; N'-(4-methylpentane-2-iriden) octadecane hydrazide produced in Production Example 16.

The rubber composition of the present invention contains a rubber component, a compound represented by the formula (1), and a compound represented by the formula (2), whereby the compound originally represented by the formula (1) is contained. While maintaining the effect of low heat generation, it suppresses the increase in Mooney viscosity and has excellent workability, so that it can be suitably used as a material for tires.

Claims (9)

A rubber composition containing the following components (a), (b) and (c).
Component (a); Rubber component component (b); Compound represented by the following formula (1) Component (c); Compound represented by the following formula (2)

[In the formula, A represents a group represented by the following formula (i) or (ii).
In formula (i) or (ii), R ¹ , R ² , R ³ and R ⁴ represent hydrogen atoms or alkyl groups having 1 to 18 carbon atoms, respectively.
X represents a nitrogen-containing heterocyclic group, an alkyl group having 1 to 5 carbon atoms, an aryl group, or a group-Y-CO-NHA. Alternatively, X may form a ring by binding to A via the group -CHR ⁶ -CR ⁵ = N-. Each of these groups and rings may further have a substituent.
Y represents a divalent nitrogen-containing heterocyclic group, an alkylene group having 1 to 18 carbon atoms, or an arylene group.
R5 has a hydrogen atom, an alkyl group having ¹ to 18 carbon atoms, or an aryl group.
R ⁶ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydrazide group, an amino group, a thiocarboxyl group, or a thiol group, and each of these groups may further have a substituent.
Z represents an alkyl group having 6 to 40 carbon atoms, and the alkyl group may further have a substituent. ]

The rubber according to claim 1, wherein the compound represented by the formula (1) is at least one selected from the group consisting of the compounds represented by the following formulas (1a), (1b), and (1c). Composition.

[In the formula, X'represents a nitrogen-containing heterocyclic group, an alkyl group having 1 to 5 carbon atoms, or an aryl group.
Y'represents a divalent nitrogen-containing heterocyclic group, an alkylene group having 1 to 18 carbon atoms, or an arylene group.
Each group represented by X'and Y'may further have a substituent.
A, R ⁵ and R ⁶ are the same as described above. ] The nitrogen-containing heterocyclic group represented by X in the formula (1) and the nitrogen-containing heterocyclic group represented by X'in the formula (1a) are a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridadinyl group, a triazolyl group and a quinolyl group. The rubber composition according to claim 1 or 2, which is at least one selected from the group consisting of an isoquinolyl group and a benzoimidazolyl group. The arylene group represented by Y in the formula (1) and the arylene group represented by Y'in the formula (1b) may be a phenylene group or a naphthylene group, and the arylene group may further have a substituent. Item 6. The rubber composition according to any one of Items 1 to 3. The rubber composition according to any one of claims 1 to 4, wherein the component (c) is a compound represented by the following formula (2a).

[In the formula, Z'is an alkyl group having 6 to 25 carbon atoms, A'is a formula (ia) or (iia), and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are hydrogen atoms or carbons, respectively. The number 1 to 6 alkyl groups are shown. ] The rubber composition according to any one of claims 1 to 5, wherein the rubber component is a diene-based rubber. The rubber composition according to any one of claims 1 to 6, further comprising the component (d) silica. A tire produced by using the rubber composition according to any one of claims 1 to 7. An additive for rubber containing the following components (b) and (c).
Component (b); Compound represented by the following formula (1) Component (c); Compound represented by the following formula (2)

[In the formula, A represents a group represented by the following formula (i) or (ii).
In formula (i) or (ii), R ¹ , R ² , R ³ and R ⁴ represent hydrogen atoms or alkyl groups having 1 to 18 carbon atoms, respectively.
X represents a nitrogen-containing heterocyclic group, an alkyl group having 1 to 5 carbon atoms, an aryl group, or a group-Y-CO-NHA. Alternatively, X may form a ring by binding to A via the group -CHR ⁶ -CR ⁵ = N-. Each of these groups and rings may further have a substituent.
Y represents a divalent nitrogen-containing heterocyclic group, an alkylene group having 1 to 18 carbon atoms, or an arylene group.
R5 has a hydrogen atom, an alkyl group having ¹ to 18 carbon atoms, or an aryl group.
R ⁶ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydrazide group, an amino group, a thiocarboxyl group, or a thiol group, and each of these groups may further have a substituent.
Z represents an alkyl group having 6 to 40 carbon atoms, and the alkyl group may further have a substituent. ]